TW201229139A - Method of manufacturing liquid crystal display device, liquid crystal display device and liquid crystal alignment agnet - Google Patents

Abstract

The present invention provides a method of manufacturing liquid crystal device which has wide field of view, quick response speed of liquid crystal compound, excellent display characteristic and long-term reliability. The present invention is a method of manufacturing liquid crystal device having step(1), step(2) and step(3). The step(1) is using liquid crystal alignment agent and forming coating film on conductive film of a pair of substrates. The liquid crystal alignment agent comprises polymer component having functional group represent by formula(A1) and functional group containing polymeric c-c double bond in same or different polymer. The step(2) is making a pair of coating films on which the coating film is formed face each other and disposing a pair of substrates interposed by liquid crystal layer in order to form liquid crystal cell. The step(3) is irradiating liquid crystal cell by light in a state where voltage is applied between conductive films of a pair of the substrates.

Description

201229139 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a method of producing a liquid crystal display element, and a liquid crystal alignment agent. More specifically, a new method for manufacturing a liquid crystal display element having a wide angle and a fast reaction speed, a liquid crystal display element manufactured by the method, and a liquid 0 suitable for the method [Prior Art] In the liquid crystal display element, 'as a vertical alignment mode The multi-domain vertical alignment type panel is formed by restricting the reversal direction of the liquid crystal molecules in the liquid crystal panel, thereby expanding the viewing angle. In this way, the transmittance of the protrusions is inevitably caused. In the recent years, in order to solve the problem of the MVA type panel, the PSA (Polymer Continuous Alignment) mode is a substrate having a patterned conductive film and a pair of substrates including a guide having no pattern. The pre-tilt angle characteristic is found by sandwiching a polymerizable liquid crystal composition with a gap or a gap between a pair of substrates having a patterned substrate, and applying a voltage between the conductive films to polymerize the polymerizable compound. The orientation direction of the crystal. According to this technique, the transmittance and contrast which are inevitable in the M VA type panel by the expansion of the viewing angle and the high-speed reaction of the liquid crystal molecules by the specific constitution are not obtained. However, in order to polymerize the above polymerizable compound, a large amount of ultraviolet rays such as 100,000 J/m2 is required, and in addition to the production, the liquid crystal is apparent in the production of MVA according to the crystal orientation agent b. Contrast 〇, proposed technology: the ultraviolet ray of the compound in the base film of the electric film, the control of the liquid into the conductive, but also the problem of the solution to the problem of the sub-decomposition of the liquid crystal sub-201229139 sub-decomposition, will also be The ultraviolet unreacted compound remains in the liquid crystal layer, which adversely affects the retention characteristics of the electric &gt;1, or the problem of the property. In contrast, the non-patent document 1 discloses a mesogen. A method of polymerizing a polyimine liquid t liquid crystal alignment film. According to Non-Patent Document i, a liquid crystal display element of a liquid crystal alignment film has a liquid crystal fast. However, in the non-patent literature, there is no record on how to use the reaction. Or, as in the case of the amount of ultraviolet irradiation, 'the pressure retention characteristic is still unavoidable. [Prior Art Document] [Non-Patent Document] [Non-Patent Document 1] Y .-j.Lee et al., SID 〇9 (2009) SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has a wide viewing angle, a liquid crystal molecule having a high reaction speed, and excellent reliability. The invention for solving the above problems is: a method for producing a liquid crystal display element, wherein (1) a liquid crystal alignment agent is used (hereinafter, a liquid crystal alignment is formed on the conductive film of a pair of substrates having a liquid conductive film) The agent contains a polymer component (hereinafter, it is said that the unpolymerized after irradiation shows unevenness in production, and the long-term use of the green plate can be used for a liquid crystal source having a reaction rate of the molecule formed by the method, and If a large characteristic is still required, especially electric DIGEST, the purpose of the 666th is to provide a characteristic and long-term can have the following steps: ? 曰 alignment agent (A), ') in the step of forming a film, as "[A The polymer is 201229139 minutes"), and the polymer component has a group containing a polymerizable carbon-carbon double bond in the same or different polymer and a group represented by the following formula (A1). (2) The above will be formed. Paint The pair of substrates are disposed in such a manner that the coating film is opposed to the liquid crystal layer, and the liquid crystal cell is formed, and (3) is applied between the pair of substrates, the lightning-guide film, and the like. a step of irradiating the liquid crystal cell with light in a state of a voltage. R3—[r2^-R1-(a 1) In the formula (A1), R1 is a methylene-phenylene group or a cyclohexylene group. These groups may be substituted. R2 is a linking group including any of double bonds. R3 is .8 is 0 or 1. An alkyl group having 2 to 30 carbon atoms, a part or all of a hydrogen atom, a di bond, an ether bond a method of producing a liquid crystal display element according to the present invention, wherein the ester bond and the oxygen have at least two monocyclic structures, that is, a coating film is formed in step 10 using a liquid crystal alignment agent containing the polymer component of the above specific structure [A] At the same time, in the step (3), the liquid crystal cell is irradiated with light while applying a voltage between the conductive films of the pair of substrates, and a liquid crystal display having a wide viewing angle, a high reaction speed of liquid crystal molecules, and excellent display characteristics and long-term reliability can be produced. element. [Α]. A polymer component is preferably a group containing a polymerizable carbon-carbon double bond of [A_丨] and a polymer having a group represented by the above formula (A1) (hereinafter, referred to as "[A-1) ]polymer"). According to the method for producing a liquid crystal display device, when the [A] polymer component contains the [A-1] polymer, the viewing angle of the obtained liquid crystal display element can be improved 201229139, the reaction speed of liquid crystal molecules, display characteristics, and long-term reliability. The polymer component [A] preferably contains [A-2] a polymer having a group having a polymerizable carbon-carbon double bond (hereinafter referred to as "[A-2] polymer,") and [eight_3 A polymer having a group represented by the above formula (A1) (hereinafter referred to as "[A3] polymer,"). According to the method for producing a liquid crystal display device, the [A] polymer component contains the [A-2] polymer and the [A-3] polymer, and the liquid crystal display device can be manufactured more easily. R3 in the above formula (A1) is preferably a group represented by the following formula (A2), «Μ书 R5VR4f (A2) Formula (A2), R4 is a stupid base, a stretched biphenyl group, an anthranyl group, and a stretch Cyclohexyl, dibicyclohexyl, cyclohexylphenyl or divalent heterocyclic. Some or all of the hydrogen atoms possessed by these groups may be substituted. R5 is a methylene group which may have a substituent in the package s, and at least one of a stretched alkyl group, a double bond, a double bond, an ether bond, an ester bond and a heterocyclic group having 2 to 2 carbon atoms, wherein The (c+1) valence group of (c+1) hydrogen atoms is removed from stupid, biphenyl, naphthalene, cyclohexane, bicyclohexyl, cyclohexyl or heterocyclic compounds. Some or all of the hydrogen atoms of the base may be substituted. &amp; 7 is a hydrogen atom, an aryl group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group. b is 0 or 1. c is an integer from 1 to 9. 4 i or 2. When r4, r5, &amp; 7 and b are each plural, a plurality of R, R5'R, and b may be the same or different from each other. According to the method for producing a liquid crystal display device, R3 of the [A] polymer component of the liquid crystal alignment agent (A) has the above-described specific structure, and the viewing angle of the liquid crystal display element and the reaction speed of the liquid crystal molecules can be further improved, and 201229139 Characteristics and long-term reliability. The [A] polymer component preferably has a polyorganosiloxane structure. According to the method for producing a liquid crystal display device, the liquid crystal alignment agent (A) has a polyorganosiloxane structure, and the light resistance of the obtained liquid crystal display element can be improved. The [A] polymer component preferably further contains at least one polymer selected from the group consisting of polyproline and polyimine. According to the method for producing a liquid crystal display device, the specific polymer is contained as the [A] polymer component, whereby the solution characteristics of the obtained liquid crystal alignment agent (A) can be improved, and the electrical characteristics of the obtained liquid crystal display element can be improved. . The present invention also includes a liquid crystal display element manufactured by the method of manufacturing a liquid crystal display element. The liquid crystal alignment agent of the present invention contains [A] a polymer component having a group containing a polymerizable carbon-carbon double bond in the same or different polymer and a group represented by the following formula (A1), RHR2^R1 - ( A1) In the formula (A1), R1 is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexyl group. Some or all of the hydrogen atoms possessed by these groups may be substituted. R2 is a linking group containing a double bond, a triple bond, a bond, a S bond, and an oxygen atom. R3 is a group having at least two single ring structures. a is 0 or 1. The liquid crystal alignment agent can be suitably used in the method for producing a liquid crystal display device because it contains a polymer component having the above specific structure. The liquid crystal display element manufactured by the manufacturing method of the present invention has a viewing angle of 201229139 and exhibits sufficient transmittance and contrast, long-term continuous operation for a long period of time, high reaction speed of liquid crystal molecules, and degree 'in the display effect is particularly good, which may impair display characteristics. . In addition, the manufacturing method according to the present invention, 无 无 无 无 无 因为 照射 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The cost is superior to the current liquid crystal display elements in two aspects, and can be suitably used in various applications including a two-dimensional display and a three-dimensional display of a liquid crystal television. [Embodiment] &lt;Manufacturing Method of Liquid Crystal Display Element&gt; The method for producing a liquid crystal display element of the present invention has the following steps: (1) a step of forming a coating film on the conductive crucible of a pair of substrates having a conductive film using a liquid crystal alignment agent, The liquid crystal alignment agent contains [A] polymer component 'the polymer component having a polymerizable carbon-carbon double bond group in the same or different polymer and a group represented by the following formula (A1); a state in which a pair of substrates on which the coating film is formed is disposed such that a pair of coating films face each other to form a liquid crystal cell, and (3) a state in which a voltage is applied between the conductive films of the pair of substrates The step of irradiating the liquid crystal cell with light is performed. Then, a liquid crystal display element can be manufactured by disposing a polarizing plate on both surfaces of the liquid crystal cell after the irradiation light obtained as described above. Next, each step will be explained. [(1) Step] 201229139 In this step, a liquid crystal alignment agent (A) containing a polymer component of [A] is used to form a coating on the conductive film of a pair of substrates having a conductive film. The liquid crystal alignment agent (A) will be described later. When manufacturing a TN type, STN type or VA type liquid crystal display element, two substrates each having a patterned transparent conductive film are provided as a pair, and on each of the transparent conductive film forming surfaces, lithographic printing is preferred. The liquid crystal alignment agent (A) is applied by a method, a spin coating method or an inkjet printing method, respectively, and then a coating film is formed by heating each coated surface. Here, as the ruthenium substrate, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (aliphatic) can be used. A transparent substrate made of plastic such as olefin). For the transparent conductive film provided on one side of the substrate, it is possible to use tin oxide (the nesa film made of Sn〇d (registered trademark of PPG, USA) and indium oxide-tin oxide (In2〇3_Sn〇2). For the film or the like, a patterned transparent conductive film can be obtained, for example, a method of forming a pattern by photolithography after forming an unpatterned transparent conductive film, a method of using a photomask having a desired pattern when forming a transparent conductive film, and the like. In the case of the alignment agent (A), in order to make the adhesion between the surface of the substrate and the transparent conductive film and the coating film better, it is also possible to apply a coating film on the surface of the substrate in advance to apply a g-functional decane compound or a functional titanium compound. After the liquid crystal alignment agent (A) is applied, in order to prevent the applied liquid crystal alignment agent, such as dimer solution, etc., the car is pre-heated (pre-baked). The pre-supply Wengui is 3〇C. ~2〇〇t, more preferably Μ15Qt, especially good 〇〇C. The preheating time is preferably 〇·25 minutes~1〇 minutes, more preferably 〇·5 minutes~5 minutes. Then, in order Completely remove the solvent, and then at --10-201229139 In the production of the polyorganosiloxane compound (A), in the production method 1, the residual dicarboxylic acid is removed, and it is preferred to carry out a calcination (post-baking) step. The temperature of the calcination (post-baking) is preferably 80 ° C to 300 ° C, more preferably 1 20 ° C to 250 ° C. The post-baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film of the film thus formed The thickness is preferably Ο.ΟΟΙμιη to Ιμιη, more preferably 0.00 5 μηι to 0.5 μιη. On the other hand, when the IPS type liquid crystal display element is manufactured, the conduction of the substrate on which the transparent conductive film forming the comb-tooth pattern is provided is provided. A liquid crystal alignment agent (A) is applied to each of the film formation surface and the opposite substrate on which the conductive film is not provided, and then the coating film is formed by heating each of the coated surfaces. The substrate and the transparent conductive film used at this time are made of a transparent conductive film. Patterning method, pretreatment of substrate, coating method of liquid crystal alignment agent (A), heating method after coating, and preferred film thickness of the formed coating film and when manufacturing the above-mentioned ΤΝ type, STN type or VA type liquid crystal display element The same. The formed film can be The λ / 乂1 is supplied to the step (2), and any rubbing treatment may be performed. The rubbing treatment may be performed by rubbing the nylon, rayon, and cotton in a direction. The coating film surface formed as described above, such as a roll of a cloth made of a fiber such as a flower, is provided with a liquid crystal molecule by a pair of coating films, and is also disclosed in Japanese Laid-Open Patent Publication No. Hei 6-222366; The alignment film is, for example, a process of changing the liquid crystal S 1 D7S44 by eight-page angle by irradiating ultraviolet rays to the partial portion of the alignment film portion of the liquid crystal alignment film, for example, 曰 示 、 、 、 、 、 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 液晶 液晶 液晶 液晶 液晶The invention is shown in the section of the liquid crystal alignment film on the surface of a liquid crystal alignment film, and the film has a crystal display unit [(2) step]. 〇 Prepare the seeding method in the relative arrangement, the pairing configuration, or the anti-parallel method. The first film is interposed between the two base spaces and the second one. Applying the alignment film surface block substrate at the formation position to produce a liquid photoresist film, and then performing a process of removing the photoresist film after rubbing different from the rubbing treatment direction, thereby making the liquid crystal alignment regions different in liquid crystal alignment energy and improving The visual field characteristics of the obtained waveware and the like. In the first step, the pair of substrates on which the coating film is formed are disposed so as to sandwich the liquid crystal layer, and two liquid crystal cells are formed as described above, and the liquid crystal alignment film is formed as described above. A liquid crystal cell is manufactured by disposing a liquid crystal between the substrates. When the film is subjected to rubbing treatment, the two substrates are in such a manner that the rubbing directions of the respective coating films are at an angle to each other. For example, in the method of forming a liquid crystal cell in a vertical direction, for example, the following two methods are conventionally known. method. First, each liquid crystal alignment gap (cell gap) was placed on opposite sides of the substrate, and the peripheral portion of the sealant was attached; the liquid crystal cell was fabricated by encapsulating the liquid crystal cell after the liquid crystal was injected into the liquid crystal by the substrate surface and the sealant. The method is a method called 0DF (0ne Drop Fill). A certain cloth of one of the two substrates of the liquid crystal alignment film, for example, an ultraviolet curable sealing material, and then liquid crystal is dropped on the liquid crystal, and then the liquid crystal alignment film is used. The other surface of the substrate is then irradiated with ultraviolet light to harden the sealant crystal unit. -12- 201229139 Wide? For the sealant, for example, an epoxy resin or the like which contains a hardener spacer and a vaporized glass can be used. For the above liquid crystal, it is preferable to use a negative dielectrically dominant nematic liquid crystal, for example, a dicyanobenzene liquid crystal, a ruthenium ruthenium, a Schiff test liquid crystal, a bismuth coupler can be used. Nitrogen-based liquid crystal, biphenyl liquid crystal, and cyclohexane liquid crystal. The thickness of the liquid crystal layer is preferably a pawl ~5_. According to any of the methods, the &amp; crystal unit manufactured as described above is further heated to a temperature at which the liquid crystal used becomes an isotropic phase, and then slowly cooled to room temperature, and it is desirable to remove the flow alignment at the time of liquid crystal filling. [(3) Step] This step _ irradiates light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. For the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 15 〇 nm to 8 〇〇 nm can be used, and ultraviolet rays containing light having a wavelength of 3 〇〇 nm to 4 〇 0 nm are preferable. As the light source for illuminating light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the above preferred wavelength region can be obtained by combining the above-mentioned light source with, for example, a filter, an optical thumb, or the like. The amount of light irradiation is preferably 1,000 J/m2 or more, less than i〇〇, 〇〇〇J/m2, more preferably i, 〇〇〇J/m2 to 50,000 J/m2. In the conventional PSA mode liquid crystal display element manufacturing, it is necessary to irradiate light of a level of 100,000 J/m 2 , but in the method of the present invention, even if the light irradiation amount is 50,000 J/m 2 or less, and further, it is 10,000 J/m 2 . In the following, a desired liquid crystal display element can be obtained, which contributes to a reduction in the manufacturing cost of the liquid crystal display element, and also can reduce the deterioration of electrical characteristics and long-term reliability caused by intense light-13-201229139. Then, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after the above treatment. In the case of the polarizing plate, a polarizing plate called a "H film" which is a side-stretched polyvinyl alcohol and which absorbs iodine, is sandwiched by a cellulose acetate protective film or a film made of a film itself. Polarizer. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent (Α) used in the method of the present invention contains a [Α] polymer component having a polymerizable carbon-carbon double bond group in the same or different polymer and The group represented by the above formula (A 1 ). Further, the liquid crystal alignment agent (A) may comprise, as the [A] polymer component, at least one polymer selected from the group consisting of polyglycine and polyimine (hereinafter, referred to as "polymer (B) ""Other polymer" described later. Further, other components may be contained insofar as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail. &lt;[A] Polymer component&gt; [A] The polymer component has a group containing a polymerizable carbon-carbon double bond in the same or different polymer and a group represented by the above formula (A1). [Base containing a polymerizable carbon-carbon double bond] Examples of the group containing a polymerizable carbon-carbon double bond include a group represented by the following formula (A), and CH 2 = C - (COO) - ( Χ^-ΙίΟ)—X11)^— (A) In the above formula (A), RA is a hydrogen atom or a fluorenyl group. -14- 201229139 X1 and x11 are each independently 1,4-phenylene, fluorenylene, 1,2-ethylene, 1,2-propyl or ι,3-extended propyl. A, B, C, and D are each independently 〇 or 1. Where 'C is 0 and D is 1, X11 is a 1,4-phenylene group. In addition, when B is 0, D is 0. Specific examples of the group represented by the above formula (A) include, for example, a vinyl group, an allyl group, a p-styryl group, a (meth) propylene fluorenyl fluorenyl group, and a 2-((meth) propylene group.醯oxy)ethyl, 3 ·((fluorenyl)propenyloxy)propyl, 4-((indolyl)propenyloxy)butyl, 5-((methyl)propenyloxy)pentyl , 6-((indenyl)propenyloxy)hexyl, 7-((indenyl)propenyloxy)heptyl, 8-((indenyl)propenyloxy)octyl, 9-((methyl)) Propylene oxime) fluorenyl, 10-((meth)acryloxy) fluorenyl, 4_(2_((indolyl) propylene oxime)ethyl)phenyl' 2_((4_(fluorenyl)) Propylene oxime)phenyl)ethyl, 4-((meth)acryloxymethyl)phenyl, 4-(methyl)propenyloxyphenyl fluorenyl, 4-(3-((A) Acryloxy)propyl)phenyl, 3-(4-(methyl)propenyloxyphenyl)propyl, 4-((indolyl)propenyloxymethoxy)phenyl, 4_ (2-((indenyl)propenyloxy)ethoxy)phenyl, 4-(3-(^methyl)acryloxy)propoxy)phenyl, (fluorenyl)propoxy A Oxymethyl, 2-((meth)propenyloxymethoxy)ethyl, 2-(2-((methyl)propenyloxy)ethoxy)ethyl, 2-(2(2) ^(/base) propylene oxime) ethoxy)ethoxy)ethyl, 3·(3_((methyl)propyl ethoxylate)propoxy)propyl, propylene methoxymethyl Wait. Among them, preferred are ethyl, allyl, p-styryl, (meth)allyloxymethyl, 2-((f-)propen(tetra)oxy)ethyl and 3 ((A) The group of the above-mentioned polymerizable carbon-carbon double bond is preferably a group represented by the above gas (A), more preferably selected from the above-exemplified specific groups. [Bases of the above formula (A1)] R1 of the above formula (A1) is a methylene group, a carbon atom having 2 to 3 Å, a stretching phenyl group or a stretching hexyl group. Some or all of the hydrogen atoms may be substituted. As the alkylene group having 2 to 30 carbon atoms represented by the above R1, it may be an extended ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Stretching Xin, stretching base, stretching base, stretching undecyl, stretching lauryl, tetradecyl, hexadecyl, octadecyl, hexadecyl, and Decaalkyl, eicosyl, tetracosyl, tetracosyl, tetracosyl, pentadecyl, hexadecyl, heptadecyl , octadecyl, hexadecyl, Decylene or the like. Among them, 'in order to stably exhibit liquid crystal alignment, hexyl, octyl, fluorenyl, decyl, dialkyl, tetradecyl, hexadecyl, nonaalkyl, The number of carbon atoms such as an eicosyl group is 5 or less. 'It is preferred to extend the pentyl group, extend the eleventh burning group, extend the ten-fold octyl burning base, extend the ten-up, and extend the R2 below 20 to contain double a linking group of a bond, a triple bond, an ether bond, an ester bond, and one of the oxygen atoms. Examples of R2 include, for example, an ethylenediyl group, an ethylidene group, an anthracenyl group, a methanediyloxy group, and a fluoromethanediyl group. And - calcined diyloxy group, etc. Further, it may contain the above-mentioned ^, ^, or may contain a combination of each bond. Further, when R1 is a phenyl group or a ring-extension, the alignment of the formed alignment film And the solubility of the solvent -16-201229139 See 'Car father's R2 contains the right 6 曱 base or the carbon number of 2 ~ 30. Also, a is 0 or 1. R3 is with $, 丨, two The base of the single-ring structure is preferably a positive or negative dielectric anisotropically-doped group. A single-ring structure means that one ring structure is independent of other ring structures. There is too much structure that does not have a ring structure and a bond with other ring structures, that is, a structure having a structure of 1τ β w ° and no condensed ring structure. In addition, in the case of a single heterocyclic ring structure, it is possible to have a structure of each month and an aromatic ring. Any of the above structural structures, the above three may also have a combination thereof. No R is particularly limited to a group having two or more single ring structures to the upper/beta, but R3 is more than (r7)tr6- { 疋杈 is a group represented by the following formula (A2). R5rR4· (A2) π In the formula (A2), 'R4 is a stretching phenyl group, a stretching phenyl group, a stretching naphthyl group, a stretching peasant soil #一娘A hexyl group, a cyclohexyl group or a divalent heterocyclic group. Some or all of the hydrogen atoms of these groups may be substituted. R5 is a linking group of a methylene group which may have a substituent and a stretching alkyl group, a double bond, a triple bond, an ether bond, an ester bond, and a heterocyclic group which may have a substituent of 2 to 1 ring. R6 is a (c+) valence group which removes (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexyl, cyclohexyl or heterocyclic compounds. This group, some of which have a hydrogen atom Part or all may be substituted. r7 is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a difluoromethoxy group or an alkylcarbonyloxy group. 〇 or 丨. c is an integer of ～9. d is 1 or 2. When each of R4, 尺7, and b is plural, a plurality of R4, R5, R7, and b may be the same or different from each other. The structure represented by the formula (A2) can further increase the electro-optical reactivity of the obtained liquid crystal 201229139 display element. In the formula (A2), it is a stretching phenyl group, a stretching phenyl group, a naphthyl group, a cyclohexylene group, and a stretching ring. The cyclohexyl group is a phenyl group or a divalent heterocyclic group. The divalent heterocyclic group may, for example, be a pyridyl group, a fluorenyl group or a pyrimidinyl group, and the above formula (A2) may be mentioned. a substituent having at least one of a stretching group, a double bond, a triple bond, an ether bond, and a heterocyclic group having a methylene group having 2 to 10 carbon atoms; and a linking group of R6 The [A] polymer component may be appropriately selected according to the desired orientation and dielectric anisotropy. Examples of R5 include methane diyl, ethane dipropane diyl, ethylene diyl, acetylene diyl, and ether. a group, a g group, a methyloxy group, an ethanediyloxy group, a fluoromethanediyloxy group, a difluoromethyloxy group, etc. Among them, an ethanediyl group, an acetylene diyl group, and a methane are preferred. Di- oxy, difluoromethanediyloxy. In addition, in the design of the side chain structure may contain R5 or may not contain. ^ In the above formula (A2), R0 is from benzene, biphenyl, naphthalene, The (c + 丨) hydrogen atom (c + 1) valence group is removed from cyclohexane hexane, cyclohexyl benzene or a heterocyclic compound. c is an integer of 1 to 9. For the ruler 6, for example, _ 1 There are the same groups as the above-mentioned divalent group of R4. In the above formula (A2), R7 is a hydrogen atom, a cyano group, a fluorine atom: a group, an alkoxycarbonyl group, an alkyl group, an &amp;oxy group, and a trifluoromethyl group. The oxycarbonyloxy group. Examples of the alkoxycarbonyl group include a methyl group, an ethoxycarbonyl group, an @oxycarbonyl group, and the like, and in the case of an alkyl group, a bovine has a methyl group, an ethyl group, a propyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and the like, and a carbon such as a butyl group or an isobutyl group is a straight bond or a branched alkyl group. In the above formula (A2), R6 has a plurality of fluorenyl groups and alkanedicarboxylic acid diester groups of 0 or 1 and capable of a trifluoropentyl carbonyl group having a number of, for example, -18 to 201229139. When the substituent (R7) is used, a different substituent may be used in combination. In the case of a combination of R having a plurality of substituents, 'in order to stably exhibit a desired dielectric anisotropy, a milk atom and a cyano group are preferred. Combination, a combination of a gas atom and a burn group, a combination of a cyano group and a burn group. Further, c is an integer of 1 to 9. &lt;Polymers [Al], [A-2], [A-3]&gt; For the [A] polymer component, it is preferred to contain [A_丨] having a polymerizable carbon-carbon double bond. A polymer having a group and a group represented by the above formula (A1). Further, in terms of the [A] component, it is also preferred that the polymer having a group containing a polymerizable carbon-carbon double bond and [A_3] have a group represented by the above formula (A1). Polymer. These polymers may have a specific polymer backbone as described above, and may be suitably selected from the group consisting of a polyorganosiloxane, a polyamidolimine, a polyamido acid, a polyacrylate, a polydecyl acrylate, and a poly(benzene). Ethylene-phenylmaleimide derivatives, cellulose derivatives, polyesters, polyamines, polystyrene derivatives, polyglycosides as main chain structures are preferred from the viewpoint of electrical characteristics. From the viewpoint of light resistance, a polyorganosiloxane (hereinafter, referred to as a polyorgano-oxygen compound (A) '') is preferred. The polyorganosiloxane compound has a polystyrene-equivalent weight average molecular weight of from 500 to 丨,000,000', more preferably from 1,000 to 100,000, still more preferably 1, as determined by gel permeation chromatography (GPC). 000~50, hehe. Such a polyorganosiloxane compound (A) can be produced by any method within the range of the above characteristics. The polyorganophyta compound (A) can be, for example, a decane compound having a poly--19-201229139-bonded carbon-carbon double bond group and an alkoxy group (hereinafter, it can be called "Shi Xiyuan compound (al) a method in which a mixture of a decane compound (al) and another alkoxy compound (al) and another alkoxydecane compound (hereinafter, may be referred to as "decane compound (a2)") is reacted in the presence of a dibasic acid and an alcohol (manufacturing method 1) Or the method of the hydrolysis/condensation (manufacturing method 2). In the above production method 1 or 2, the crushed compound (a2) is used in addition to the compound (a1), and as a decane compound (a2) A part of the decane compound having a group represented by the above formula (A1) and an alkoxy group (hereinafter referred to as "decane compound (a2-1)") can be obtained in a polymerizable carbon-containing anti-double bond. Further, the polyorganosiloxane compound (A) having a structure represented by the above formula (A1) is further contained. Further, the polyorganosiloxane compound (A) can also be produced as follows: In the above production method 1 or 2 'Use Shixi Burning Compound outside the Shixi Burning Compound (ai) And (a2), and a decane compound having an epoxy group and an alkoxy group (hereinafter, may be referred to as "the smelting compound (a2-2)")) as the at least a part of the decane compound (a2), which is first synthesized and has a a polymerizable carbon, a carbon double bond group and an epoxy group polyorganosiloxane (hereinafter, may be referred to as "polyorganooxazee front buckle (A)"), and then comprising and having the above formula (Ai) a method of reacting a carboxylic acid having a base and a carboxyl group (hereinafter, referred to as "specific carboxylic acid 2") (manufacturing method 3), or in the production method 1 or 2, using as a raw material The decane compound (a2) of the decane compound (a2-l), firstly synthesizing a polyorganosiloxane having an epoxy group (hereinafter, may be referred to as "polyorganosiloxane (A) precursor)", followed by A method of reacting a specific carboxylic acid 2 and/or a carboxylic acid containing a compound having a polymerizable carbon-carbon double bond and a carboxyl group (hereinafter, may be referred to as "specific carboxylic acid 1") (Production Method 4). , 201229139 For any of the above cases, as a decane compound (a2) The alkane compound (a2-l) and the decane compound (a2) other than the decane compound (a2-2) (hereinafter may be referred to as "decane compound (a2_3),) are used in combination with hydrazine as the above-mentioned calcining compound (al)' A compound represented by the following formula (a-Ι) can be cited. • Ra CH2==C—(Co°)a—(X1)^0)'XJI)^;~Si(ORB)4.E (a-1) In the above formula (a-1), ra, Xi, Xi丨, a, B, C and D are the same as defined in the above formula (A). Rb is an alkyl group having 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. e is an integer β of 1 to 3, and in the above formula (a-1), the alkyl group having a carbon number of 丨 to 12 in terms of re is preferably an alkyl group having a carbon number, and specific examples thereof include The mercapto group, the ethyl group, the n-propyl group, the n-butyl group, the second butyl group, the third butyl group and the like are preferably a methyl group, an ethyl group or a n-propyl group, and particularly preferably an ethyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by Ri include benzoquinone, methyl strepyl and the like. &amp; E in the above formula (al) is preferably 1 or 2, and particularly preferably i. Specific examples of the decane compound (al) include, for example, vinyl trimethoxy decane, vinyl triethoxy decane vinyl tripropoxy decane, vinyl triisopropoxy decane, and vinyl trisole. n-Butyloxyzide, Vinyl Triisobutoxy Dream, Ethylene, Third Cetaceous, Allyl Trimethoxy, Allyl Triethoxy, Dipropyl Propoxy decane, allyl triisopropoxy decane, olefinic diyl 3--21 - 201229139 n-butoxy fluorene, allyl tris-butyl phthalate, π-material, butyl decane, allyl 3rd third butyl milk base burning, the present ethylene ternary trioxetine, p-styryl triethoxy decane, p-styryl tri-a ^ Α ^ ^ ^ internal rolling decane, p-styryl Triterpenoid - S -Γ tr Α ^ ^ soil-n-butoxy decane, p-styryl diisobutoxy decane, p-benzene benzene A, work must reduce soil - second butoxy decane, (A Alkyl methoxymethyl triterpene „ φ . . ^ A alkane, (meth) propylene methoxymethyl diethoxy sulphur, (meth), (r-)醯 methoxymethyl tri-n-propoxy decane, (meth) propylene methoxymethyl bis 2 | a propoxy decane, (meth) propylene decyl fluorenyl tri-n-butyl condensate (Sub) propylene methoxy methoxypropyl tri-tert-butoxy decane, 2-(methyl) propylene methoxyethyl trimethoxy oxalate, 2-(indenyl) propylene oxyethyl Triethoxy zebra, 2_(methyl) propylene oxyethyl tri-n-propoxy ketone, 2_(methyl) propyl decyloxyethyl triisopropoxy decane, 2-(methyl Acryloxyethyltri-n-butoxylate, 2-(methyl)propyloxyethylidene tri-tert-butoxydecane, 3-(indenyl)propeneoxypropane Tris-methoxy decane, 3-(indenyl) propylene methoxy propyl triethoxy decane, 3-(indenyl) propylene oxypropyl tri-n-propoxy decane, 3-(methyl) propylene oxime Oxypropyl triisopropoxy decane, 3-(indenyl) propylene oxypropyl tri-n-butoxy decane, 3-(methyl) propylene oxypropyl tri-tert-butoxy decane, 4_ (fluorenyl) propylene oxybutyl dimethoxy decane, 4-(methyl) propylene oxime Butyl triethoxy fluorene, 4-(methyl) propylene oxy butyl tri-n-propoxy oxalate, 4 _ (mercapto) propylene oxybutyl triisopropoxy decane, 4_ (Meth) propylene methoxy butyl di-n-butoxy decane, 4-(methyl) propylene oxy butyl propyl tri-second butoxy decane, 5-(indenyl) propylene methoxy pentane Tris-decyloxydecane, 5-(indenyl)propenyloxypentyltriethoxydecane, 5·(fluorenyl)propene oxime-22- 201229139=yltri-n-propoxyethanol, 5-(f-based ) propylene oxydecane, 5-(methicone decyloxypentyl tri-n-butoxy decane, 5-(::) propylene oxypentyl propyl tri-second butoxide oxylate: dilute oxygen Ethyl hexyl methoxy sulphate, fluorenylmethyl) propylene oxyhexyl) oxycarbazide, 6-(fluorenyl) propylene methoxy hexyl tri-n-propoxy oxazide (oxymethyl group) Γ: Λ ,, 丙美 _ soil monobutoxy decane, 6-(fluorenyl) propylene methoxy hexyl group, etc.: di-first butoxy decane, propylene methoxymethyl trimethoxy decane: - You can choose more than one to use. More preferably, it is a mixture of vinyl methoxy decane, vinyl triethoxy decane, allyl trimethoxy oxy, 'mono- allyl diethoxy decane, p-styryl trimethoxy decane Vinyl triethoxy decane, (fluorenyl) propylene methoxymethyl trioxy decane, 2-(indenyl) propylene methoxyethyl trimethoxy decane and (meth) acryloxy group More than one type consisting of propyltrimethoxydecane. The Dream Compound (a2-l) is a decane compound having a thiophene-indenyl group represented by the above formula (Α1), and may be used in combination with a decane compound represented by the following formula (a2_ia). (RC)f(RD)gSi(ORE)4_f.g (a2-la) In the above formula (a2-la), 'Rc is an alkyl group having 4 to 3 carbon atoms, and a fluorination having 1 to 30 carbon atoms An alkyl group, or a nicotinyl group having a steroid group having a carbon number of 51, an alkoxyphenyl group having an alkoxy group having 2 to 24 carbon atoms, or a carbon atom having a dicyclohexane skeleton of 12 to 30 Hydrocarbyl group. RD is an alkyl group having 1 to 3 carbon atoms. RE is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. -23- 201229139 f is an integer from 1 to 3. g is an integer of 〇~2. Wherein f + g ^ 3 ° is the same as the group described in the above formula (a 1) which the RC ' in the above formula (a2-1 a) and the polyorganoanthracene compound (A) can optionally have. It is preferably a methyl group in terms of Rd. For Re ' is the same as rB in the above formula (a_i). f is preferably 1, and g is preferably 〇 or 1. The cerium compound represented by the above formula (a2-la) can be exemplified as follows: For a decane compound having an alkyl group having 4 to 30 carbon atoms, for example, n-butyltrioxane can be cited. Base decane, n-butyltriethoxy decane, n-butyl tri-n-propoxy oxysphate, n-butyl triisopropoxy sinter, n-butyl tri-n-butoxy decane, n-butyl tri-second Butoxy decane, n-butyl tri-n-pentyloxy decane, n-butyl tri-second butoxy decane, n-butyltriphenoxydecane, n-pentyltrimethoxy decane, n-pentyltriethyl hydrazine Basestone, n-pentyltriphenoxydecane, hexyltrimethoxy decane, hexyldiethoxy oxacyclohexane, heptyltrimethoxy decane, heptyltriethoxy decane, n-octyltrioxane Basear, n-decyltrimethoxy decane, n-dodecyltrimethoxydecane, n-octadecyltrimethoxydecane, and the like. Further, 'for a decane compound having a fluorinated alkyl group having a carbon number of 丨~3 ', for example, 3,3,3-trifluoropropyltrimethoxy decane, 3,3,3-trifluoro can be cited. Propyltriethoxydecane, 2_(trifluoromethyl)ethyltrimethoxy-Xiyuan 2-(perfluoro-n-propyl)ethyltrimethoxy oxime, 2_(perfluoro-positive

Hexyl)ethyltrimethoxy decane, 2-(perfluoro-n-octyl)ethyltrimethoxy decane, and the like. A. For the decane compound having a hydrocarbon group having a hydrocarbon group of 17 to 51, for example, a cholesteryl trimethoxy oxime = -24-201229139 or a 3-cholesteryl triethoxy group can be cited. Base decane, 3_cholesteryl tri-n-propoxy oxacycloline, 3-cholesteryl triisopropoxy decane, 3-cholesteryl tri-n-butoxy decane, 3-cholesteryl three Second butoxy decane, 3-bilidyl alkenyl trimethoxy decane, and the like. Examples of the calcined compound having an alkoxy group having an alkoxy group having 2 to 24 carbon atoms include, for example, 4-pentyloxyphenyltrimethoxy decane and 4-pentyloxyphenyl three. Ethoxy decane, 4-hexyloxyphenyltrimethoxine, 4-octyloxyphenyltrimethoxydecane, 4-dodecyloxyphenyltrimethoxydecane, and the like. Soil The above decane compound (a2-2) is an alkylene compound having an epoxy group and an alkoxy group, and is preferably a compound represented by the following formula (a2_2). (RF)h(RG)iSi(〇RH)4.h_i (a2.2) In the above formula (a2-2), rf is a monovalent group having an epoxy group. It is an alkyl group having 1 to 3 carbon atoms. RH is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.匕 is an integer from 1 to 3. i is an integer of 〇~2. Among them, h + i$3. The Rf in the formula (a2-2) may, for example, be a 3-glycidoxypropyl group or a 2-(3,4-epoxycyclohexyl)ethyl group. In the case of Han (3, preferably = methyl group. For RH' and the above formula h, it is preferred that the plant i is preferably 0 or 1. For a specific example of the Shi Xixuan compound (a2-2), for example It can be exemplified by 3_methoxypropoxypropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmercaptodimethoxydecane, oxime = oxygen Propoxypropylmethyldiethoxydecane, 3_glycidoxypropyl 2 decyloxydecane, 3_glycidoxypropyldidecylethoxy oxime = -25- 201229139, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, etc., one or more of which may be selected The decane compound (a2_3) is a cerium compound (a2) other than the decane compound (a2-l) and (a2-2), and examples thereof include a decane compound represented by the following formula (a2-3). (a2-3) 'Rp is an alkyl group or a stupid group having 1 to 3 carbon atoms. An alkyl group of 12 or 12 or an aryl group having 6 to 12 carbon atoms. j (RP) jSi(〇RQ)4_. In (a2-3), RQ is an integer having a carbon number of 1 to 0 to 3. In the above formula (a2-3) rQ is the same as rb in the above formula (a.). In the specific example of the compound (a2_3), a compound which is ruthenium: for example, tetramethoxy decane, tetraethoxy decane, or the like N-propoxy decane, tetraisopropoxy decane, tetra-butoxy decane, tetra-n-butoxy decane, tetra-butoxy decane, etc.. A compound wherein J is 1, for example, fluorenyl-trimethyl Oxydecane, decyl monoethoxy decane, decyl tri-n-propoxy decane, decyl triisopropoxy decane, decyl tri-n-butoxy decane, decyl tri-n-butoxy decanemethyl Di-n-pentyloxydecane, methyltri-n-butoxydecane, decyltriphenoxydecane, methyltri-p-methylphenoxydecane, ethyltrimethoxyacetate, n-propyltrimethoxy And a compound of a phenyl trimethoxy sulphate or the like; a compound of a sulphur, a diiso-ethyldiethyl j is 2, and examples thereof include a diindenyl group, a diethyl decyloxy decane, and a di-n-butyl group. Propyldimethoxypropyldimethoxydecane, dimethyldiethoxydecane-26-201229139 oxydecane, etc. Compounds wherein j is 3, examples Examples thereof include trimethyl decyloxy oxime, diethyl methoxy sulfonium, tri-n-propyl decyloxy oxe, triisopropyl decyl decane, tridecyl ethoxy decane, and triethyl. Ethoxy decane or the like. Among them, a compound of the above formula (a2_3) wherein j is ruthenium or 1, more preferably ethyltrimethoxydecane, ethyltriethoxydecane or methyldioxime The base decane, decyltriethoxy decane, tetradecyloxydecane and tetraethoxy decane are particularly preferably compounds of the above formula (a2 3) wherein j is ruthenium, preferably tetradecyloxydecane and tetraethylidene. When the polyorganosiloxane compound (A) is produced by the production method 1 or 2, the decane compound used as a raw material preferably contains 1 mol% or more, more preferably, based on the total amount of the decane compound. 1 mole % ~ 60 moles / 〇, further preferably containing 2 moles %, particularly preferably containing 2 moles % ~ 30 mole % of the above decane compound (al). By the production method 1 or 2, when the polyorganosiloxane compound (A) having a group represented by the above formula (A1) is contained in addition to the polymerizable carbon-carbon double bond, the decane compound (6) is used at a time of Decane compound (4)]). At this time, the use ratio of the compound (a2)) is preferably 60 mol% or less, more preferably 5 mol% to 5 mol%, and particularly preferably 1 mol%. Ear %~40% of the ear. In the manufacturing method 1 or 2, it is preferable that the mass transfer station is in addition to the above-described decane compound, and -=3 uses a decane compound; the ratio is relative to the decane compound, preferably 60 mol. Ear% or less, more estimated 0/, more preferably 〇mol%~40mol/〇, especially good for 0%%~20mol%. When Wu Dou manufactures polyorganophosphorus oxide compound (A) by the manufacturing method 3, 201229139 'The decane a 铷 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫More preferably, it contains 1 mole. /. ～ 〇 、 , 0 30 摩尔 / 〇 矽 矽 化合物 矽 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 矽 矽 矽 ( ( ( ( ( ( ( ( ( ( ( The ratio of use of (a2_2) is relative to the king of the calcined compound, preferably 10 mol% or more, more preferably 2 mol% to 9 mol%, and is preferably 30 mol% to 70 mol%. When the polyorganosiloxane compound (A) is produced by the production method 4, the decane compound used as a raw material is preferably 2 〇 mol% or more, more preferably contained in the entire decane compound. 40 mol% of the above decane compound (a2-2). Processes 3 and 4 t, preferably without using a decane compound (a2_3) polyorganosiloxane compound (A), polyorganosiloxane precursor (A) , or H · · ' ~ Λ organic oxoxane precursor (A") can be obtained by reacting the above decane compound in the presence of an acid and an alcohol (manufacturing method 1), or hydrolysis. Method (manufacturing method 2) to manufacture. 1 and the production method 2. [Production Method 1] The production method 1 is a method in which the above decane compound is reacted in the presence of a dicarboxylic acid and an alcohol. Examples of the dibasic acid used herein include oxalic acid, malonic acid, and carbon. a compound obtained by bonding two carboxyl groups to an alkyl group having 2 to 4 atoms, benzene-28-201229139-carboxylic acid, etc. Specific examples thereof include oxalic acid, malonic acid, succinic acid, valeric acid, and hexanic acid. The acid, the o-dicarboxylic acid, the isophthalic acid, the isophthalic acid, and the like are preferably one or more of them. Particularly preferred is oxalic acid: in terms of the ratio of use of the dicarboxylic acid, the use of the decane compound as a raw material The amount of the alkoxy group is preferably from 0.2 moles to 2. moles, more preferably from 5 moles to 15 moles. The mercapto alcohol can be suitably used, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, rivet tweezers, second butanol 't-butanol, n-pentanol, and isopenic Alcohol, butanol, third pentanol, 3-methoxybutanol, n-hexanol di-p-ethylbutanol: g -3, n-octanol, 2-ethylhexanol, methyl positive =, 6-methylheptanol_4, n-nonanol, phenol, ring production &gt;335--®«: =7^ 〒基% Alcohol, one of the decyl alcohol 'benzyl alcohol, diacetone alcohol, etc., one or more of them are selected to make the alcohol of the 乂 乂 攸匕 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The aliphatic monohydric alcohol is more preferably used from the group consisting of methanol, isopropyl alcohol, n-propanol, isobutyl alcohol, and ethanol, selected from the group consisting of 七7 spear-butanol. The selected ones are selected from the group of the above-mentioned groups. The ratio of the use of the alcohol in the production method 1 and the total amount of the liquid, the amount of the liquid is 矽 化 人 〜 〜 〜 〜 More preferably, it is preferably 3 mass scoops and accounts for 25 mass% to 70 masses. The reaction temperature is preferably ~(10). c, more ^ time is preferably 0.5 hours ~ 24, + von 5 C ~ 8 〇. Hey. The reaction is (4) hours, more preferably 1 hour. In the production method 1, it is preferably ～8 hours. . No other solvent is used -29- 201229139 In the production method 1, the ruthenium ruthenium is synthesized by the reaction of the octanic compound and the sulphonic acid to form a ruthenium compound (al). Condenser body oxime. a) co-condensate with decane compound (a2)

[Production Method 2J Production Method 2 θ This hydrolysis/reduction 2 is a method for hydrolyzing and condensing the above decane compound. The compound and water are reacted in an organic solvent in the presence of a preferred catalyst in the presence of a preferred catalyst. The ratio of the compounding == is preferably used as the raw material (four), seven moles, and the total amount of the alkoxy groups, which is a molar amount. 5 Moer et al. Ershi:::Γ, can be listed as acid, test, metal compounds, salt, bismuth, and 5, for example, can be listed, acetic acid, formic acid, oxalic acid, maleic acid and so on. The inorganic base and the organic base may be exemplified by ammonia, 0β &amp; type, inorganic base, ethanol sodium: potassium hydroxide, sodium methoxide, potassium methoxide, tri-n-butylamine, 4_2:-ethylamine, diamine, tetramethylammonium hydroxide, etc. 』Based on the third-order, such as a metal compound, such as an energy compound, etc. The bovine has a titanium compound, a mis-catalyst The ratio of use is relative to 100 parts by mass, preferably 10 parts by mass, and the amount of parts used by the Shi Xixuan compound is ~ (four) parts, and the step-by-step is better (four) amount of two good _, lining ~ 1 In the above-mentioned organic solvent, for example, an alcohol, a ketone, a guanamine, an ester, and other aprotic compounds can be cited. In the case of the above alcohol, an alcohol having one hydroxyl group can be used, and a plurality of alcohols can be used. Any one of the hydroxyl group and the alcohol having a plurality of hydroxyl groups. For the above ketone, a monoketone and a β-diketone are preferably used. In the specific example of such an organic solvent, there is one hydroxyl group. Examples of the alcohol include decyl alcohol, ethanol, n-propanol, isopropanol, and Butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, third pentanol, 3-methoxybutanol, n-hexanol, 2 - Mercaptool, 2-ethylbutanol, heptanol-3, n-octanol, 2-ethylhexanol, n-nonanone, 2,6-dimercaptoheptan-4, n-nonanol, phenol, Cyclohexanol, methylcyclohexanol, 3,3,5-tridecylcyclohexanol, benzyl alcohol, diacetone alcohol, etc., and examples of the alcohol having a plurality of hydroxyl groups, for example, ethylene glycol, 1 , 2-propanediol, 1,3-butanediol, pentanediol-2,4,2-decylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2 Ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc., and a partial ester of an alcohol having a plurality of hydroxyl groups, for example, an ethylene glycol single Methyl 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-ethylbutyl ether, diethyl Glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc. Further, as for the single S, for example, acetone and acetophenone can be cited. , methyl-n-propanone, decyl-n-butanone, diethyl ketone, decyl-isobutyl ketone, methyl-31 - 201229139 keto-n-pentanone, ethyl-n-butanone, methyl-n-hexanone, two - isobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, nonylcyclohexanone, 2,4-pentanedione, acetone acetophenone S, acetophenone, poetry @ equivalent, Examples of the β-diketone include acetamidine, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, and 3,5. -octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-nonyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5- Examples thereof include heptane, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, and the like, and the guanamine may, for example, bemethantamine or fluorenyl decyl decylamine. Ν, Ν-dimethylformamide, Ν-ethyl decylamine, hydrazine, hydrazine-diethyl decylamine, acetamidine, hydrazine-mercaptoacetamide, hydrazine, hydrazine-dihydrazino Acetamide, Ν-B As acetamide, Ν, Ν- acetyl diethyl amine, Ν- Yue-yl propan Amides, Ν- methyl. Bilo. Ketone, Ν-曱 咮 咮 Ν, Ν-formate base 0 辰. Ding, Ν-甲醯基. Ratio ° π Ν, Ν - 醯 醯 味 味 Ν Ν Ν Ν Ν 乙 乙 乙 乙 乙 乙 乙 乙 Ν Ν Ν Ν Ν Ν Ν Ν ratio. Each bite and so on. For the purpose, for example, there may be mentioned a carbonic acid, a carbonic acid, a propylene carbonate, a diethyl carbonate, a methyl carbonate, an ethyl acetate, a γ-butyrolactone, and a γ-valerolactone. , n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxy butyl acetate, cesium acetate Amyl pentyl ester, 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, decyl cyclohexyl acetate, n-decyl acetate, decyl acetate, acetonitrile Ethyl ester, ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monoterpene ether , propylene glycol monoethyl ether acetate, -32- 201229139 propylene glycol monopropyl ether acetate, acetic acid propyl acetonide, early butyl ether, dipropylene-previous decyl ether, dipropylene glycol monoethyl ether, _ 蛑 ^ ^ - ethylene glycol acetate , acetamidine® oxydiethylenediester, propionate B, ^ 曰 内 &amp; n-butyl ester, isoamyl propionate di , oxalic acid-n-butyl t-hydrazine, sodium cinnamate-n-butyl sulfonate, porphyrin vinegar, butyl acetate-n-butyl acrylate, n-amyl lactate, ritual «, ethyl ethyl ester, phthalic acid-methyl ketone, Diethyl phthalate and the like. : For other aprotic solvents, for example, acetonitrile, di-N'N'N''N'-tetraethyl continuation amine, hexamethylamine, methyl phenanthrene, N-WNWN_~: two, Wn ethyl _, · dimethyl. Bottom listening, ~:: azole, N•methyl_4_piperidone, thiol-2-piperidone 1 methyl-2-° ratio π-butanone, J 3_di-methyl- 2-imidazolidinone, anthracene, 3-ditetrahydro-2(1H)-pyrimidine and the like. The use of organic solvents! _ 夕 ..., proportion and Lu 'reaction solution in the organic solvent accounted for the reaction; the proportion of the total amount of gluten is preferably Xia Wu amount j ~ 9 〇 amount%, more preferably 1 〇 mass% ~ 7 〇 quality%. In the method 2, water added at the time of production of the polyorganosiloxane, °, a gate is intermittently or continuously added to the raw material calcining compound or a solution in which the decane compound is dissolved in the organic core. The catalyst may be previously added to the raw material decane compound or in an organic solvent, in a solution of the ruthenium compound, or dissolved or dispersed in the added water. The reaction temperature is preferably from 1 ° C to loot, more preferably from 15 ° C to 80 ° C. The reaction time is preferably from 5 hours to 24 hours, more preferably from 1 hour to 8 hours. In the method for producing the organoaluminoxane compound (A), when the method 1 or 2 is carried out in the manner of -33 to 201229139, as described above, the polyorganosiloxane compound (A) having the poly(A) fluorene can be obtained. In the case of the production method 3, the polyorganopine obtained as described above is reacted with a carboxylic acid containing a specific carboxylic acid 2 to obtain a polymer (A). In the production method 4 of the polyorganosiloxane compound (A), the polyorganism obtained as described above is further mixed with a polyorganosiloxane compound containing a specific carboxylic acid ruthenium and/or a specific carboxylic acid 2 (A) ). [Reaction of polyorganooxalate precursor (A,) with a slow acid] The specific tickic acid 2 used in the production method 3 is a compound represented by a base and a rear group. The specific carboxylic acid 2 used in the production method 3 has a slow-group compound represented by the following formula (A1-C).

R3'~fR2'l7'Rl'~T]-OH II (A1-C) _ In the above formula (Al_c), R丨 is a methylene group, an alkyl group, a phenyl group or a cyclohexene group. These bases; or all of them can be replaced. R2 is a linking group containing a double bond: any of oxygen atoms. The foundation of the structure. a is a ruthenium or a structure having a dielectric anisotropy introduced as a phase of a polyorganosiloxane having a reaction between an epoxy group and a group. In the case of the machine-based oxygen-burning compound method, the oxonane precursor (A') and the organooxane compound method are used, and the oxoxane precursor (A") acid reaction can be obtained. In the formula (A1), a partial bond, an ether bond, or an ester bond having a hydrogen atom having an atomic number of 2 to 30 can be exemplified, and at least two single ring nodes can be easily used as the above formula (A1-C)- For the specific carboxylic acid 2, for example, a compound represented by the following formulas (D-1) to (D-25) can be cited. r4ch Seven COOH (D-1) R3^Ch2)-〇. R3 -〇-(cH2)-COOH (D-2)m ,, ϊ /=\ -COOH (D-17)

-COOH (D-16) R3-0 —Ί~(CH7 COOH(D - 3)R3 fly V~(CH VII COOH (0-4) R3^^{CH2 COOH (D-5) R3_〇_ (CH2)-〇. 0 0 R3 —O—L(cH2)-J—0-

o R3-0-L (ch2

-COOH (D-18) R3w. Minute C00H (D-19)

0II -COOH (D-20) R3 CH-

-COOH (D-8) R3 —0-{cH2}^0· -COOH (D-9) R3—(CH 七 O- -COOH (D-21

0 -COOH (D-22>

-COOH ( D - 25 ) R3 —0~(CH2)^—O—^>—COOH ( D· 12 &gt; r3_=_^Ch2^—〇. COOH (D-13)

o oJL r3-o-L(CH2)J-o R3 〇Mch2}Jo -COOH (D-14) R3--(cH2); COOH (D-15) The above formula (D-1)~(D- In 25), R3 has the same definition as the above formula (A lC). 111 is an integer of 1 to 30. In the case of the group represented by the above formula (A2), for example, the groups represented by the following formulae (E-1) to (E-123) can be cited.

-36- 201229139

-37- 201229139

-38- 201229139

CN F F

ξ (e-55&gt;

F F

39- 201229139

-40- 201229139

R

(6-85)

R

(E-86)

(E-87) (E-88)

(E-89) (E-90) (E-91)

R

(E - 92 )

R

F X X R

(E-94) (E - 93 )

108) 109) 110 ) 111 ) -41 - 201229139

:-112) (E-113) (E-114) •-115) (E-116) ϊ&quot;ΗΟ~ν^_^0^-(ε· 118) (E-119)

•121 :

(E-122) (E-123) In the above formula (E-1) to (E-123), R is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. X is each independently a hydrogen atom or a fluorine atom. The alkyl group having 1 to 20 carbon atoms represented by the above R may, for example, be a mercapto group, an ethyl group, a propyl group, a n-butyl group, an isobutyl group, a n-pentyl group or a n-hexyl group as a carbon atom. The alkoxy group of 1 to 20 may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a butoxy group. [Synthesis method of specific acid retardation] The order of synthesis of the specific carboxylic acid is not particularly limited, and it can be carried out by a combination of conventional methods. With respect to the synthetic sequence represented, for example, (1) a compound having a phenol skeleton and a compound in which an alkyl chain moiety of a higher fatty acid ester is substituted with an i-acid are reacted under basic conditions, and the hydroxyl group of the skeleton is unexpectedly observed. And a dentate-substituted carbon forms a bond 'and then reduces the ester to obtain a specific carboxylic acid; (2) reacts a compound having a phenol skeleton with ethylene carbonate to form a terminal alcohol compound, the hydroxyl group and the phenylsulfonate -42- 201229139 Reaction and activation 'The reaction then reacts with the hydroxyl-containing methyl benzoate to remove the sulfonyl moiety, while the hydroxyl group of the terminal alcohol compound and the hydroxyl group of the methyl benzoate as a substituent A method of generating a bond, followed by reduction of the ester to obtain a specific carboxylic acid, and the like. However, the synthesis method of the specific carboxylic acid is not limited to this. In the production method 3, only a specific carboxylic acid 2 may be used as the carboxylic acid, or a part of the specific carboxylic acid may be substituted with a compound represented by the following formula (4) within a range not impairing the effects of the present invention. At this time, the synthesis of the polyorganooxy siloxane compound (A) is carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of the hydrazine 2 and a compound represented by the following formula (4) to carry out A1-L. 〇~l1 In the above formula (4), A1 is a linear or branched alkyl group having 1 to 30 carbon atoms which may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group. a hydrocarbon group having 10 to 7 1 carbon atoms per alkyl group or having a steroid skeleton. A part or all of the hydrogen atom of the above alkyl group and alkoxy group may be substituted with a substituent such as a cyanogen group or a trifluoromethyl group. L0 is a single bond, 〇^%-◦-, -COO- or -OCO-o L1 is a single bond, a β-methyl group, a carbon atom number of 2 to 2 0, a stretching group, a stretching group, a stretching phenyl group, a hydrazine group t ρ Α ^ β , II.± 甲-hexyl, dianylene or a group represented by the following formula (ιΛι) or (L -2). Ζ is formed by reacting with an epoxy group in a compound of argon oxide (Α). A monovalent organic group of a base. /, when the middle B is a single key, L0 is a single key. -43 - 201229139

* ( L1 -1 ) * ( L1 - 2 ) The combination of the bands in the above formulae (L1-:!) and (1^-2) is preferably a carboxyl group. In the above formula (4), examples of the alkyl group having 1 to 1 or a branched chain represented by A 1 include a mercapto group, an ethyl isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. Base, n-butyl butyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylhexyl, 4-decylpentyl, 3-methylpentyl, 2-methylpentyl, 3,3-dimercaptobutyl, 2,3-dimercaptobutyl, 1,3-, 2,2-dimercaptobutyl, 1,2-dimethylbutyl, 1,2-di 1,]-dimercaptobutyl, n-heptyl, 5-nonylhexyl, 4-methylmethylhexyl, 2-methylhexyl, 1-decylhexyl, 4,4-di 3,4-diindole Pentyl, 2,4-didecylpentyl, 1,4-dioxane, dimercaptopentyl, 2,3-didecylpentyl, 1,3-didecyldecylpentyl, 1 ,2-dimethylpentyl, 1,1-dimethylpentyl |nonylbutyl, 1,3,3'-tridecylbutyl, 1,2,3-tridecyl, 6-fluorene Hepeptyl, 5-decylheptyl, 4-decylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-group, n-decyl, n-xyl Burning base, Zheng Shi Xuan • Keji, Zheng fifteen base, Zhengliuzhu base, Zheng seventeen base Linear 'n-propyl' pentyl, 3-methylpropyl, n-, 1-methylpentadienylbutyl decyl butyl, hexyl hexyl, 3-methylpentyl group with Z-bond 30 , k-pentyl, 3,3-yl, 2,2-di, 2,3,3-tributyl, n-octyl 3-mercaptoheptyl fluorenyl, n-decene, n-tetradecyl, n-eight Burning -44- 201229139 base, positive nineteen base. 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 or a cyclooctyl group. , cyclodecyl, cyclodecyl, cyclododecyl and the like. The hydrocarbon group having a carbon number of 7 to 5 1 having a steroid skeleton, for example, a group represented by the following formulas (H-1) to (H-3).

With respect to A 1 in the above formula (4), an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, and the above formula (H-1) or (H- are preferable. 3) The base. The compound represented by the above formula (4) is preferably a compound represented by the following formula (4-1) to (4 to 6). -45- 201229139

CuF2u+i CvHZtf — COOH (4-1}

CwH2w+1——COOH (4-2)

In the above formulae (4-1) to (4-6), u is an integer of 1 to 5. V is an integer from 1 to 18. w is an integer from 1 to 20. k is an integer of 1 to 5. p is 0 or 1. q is an integer from 0 to 18. r is an integer from 0 to 18. Each of s and t is independently an integer of 0 to 2, and among these compounds, a compound represented by the following formulas (5-1) to (5-7) is more preferable. -46 - 201229139

The compound represented by the above formula (4) is a compound which simultaneously reacts with a specific carboxylic acid and a polyorganosiloxane having an epoxy group, and imparts a position of a pretilt angle to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4) is referred to as "other pretilt angle-developing compound" below. In the present invention, when a specific carboxylic acid and other pretilt-developing compounds are used at the same time, the total of the specific carboxylic acid and other pretilt-developing compounds -47-201229139 is used in a ratio relative to the oxime-polyorganosiloxane. It is 0.001 m 2 to 15 m, and more preferably further 0.05 m to 〇.9 m. In this case, it is disadvantageous that the high-speed reactivity of the compound in the range of 50 mol% or less with respect to the specific carboxylic acid is more than 50 mol%, and the use ratio of the present compound exceeds 75 mol/❶. The situation of influence. For example, in the presence of a polyorganooxane precursor (A,) and a reaction catalyst of a carboxylic acid and a suitable organic solvent, for example, a polyorganosiloxane precursor (A,) and a carboxylic acid former, for example, A so-called hardening-promoting catalyst which reacts with an organic base, an oxygen compound and an acid anhydride is suitably used. With respect to the above organic base, examples of the secondary organic amine, tertiary organic amine, and quaternary organic compound, for example, the above-mentioned hardening accelerator, for example, can be classified as a tertiary organic amine of an organic base), an imidazole derivative, and a fourth-order Examples of the scale salt, the diterpene bicyclic olefin, the organometallic grade, the metallized product, and the latent accelerator accelerator hardening accelerator include, for example, a high hardening accelerator (for example, an amine addition accelerator). Hardening accelerator, amine salt type latent hardener-inducing thermal cationic polymerization type latent hardening accelerator For the specific example of the catalyst, the upper amine can be exemplified by ethylamine, diethylamine, ruthenium, . ratio. Each. For some epoxy groups • 01 moles to 1 mole, other pretilt angles appear [good for 75 moles to . Other pretilt angles 'will be better for liquid crystals'. The nucleus used in the reaction can also be used as a promoter to promote the use of a primary amine salt. There are tertiary amines (except, organic dish compound compounds, _ four, etc.. Potential latent melting point potential, microcapsule potential latent agent, high temperature dissociation, etc.. Primary or secondary organic, 派.定,β比洛Bite-48- 201229139 The above tertiary organic amines may, for example, be triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, di-bicyclobicyclo π-carbene, etc. The organic amine salt may, for example, be tetramethylammonium hydroxide or the like. The above tertiary amine (except for the tertiary organic amine as an organic base) may, for example, be benzyldimethylamine or 2,4,6-gin. (dimethylaminomethyl) phenol, cyclohexyldiamine, triethanolamine, etc. The above-mentioned D-salt derivative may, for example, be a 2-mercapto D-m. 2 - Orthodecyl sulphide α, 2-phenyl-phenyl 11 m. Sit, 2-phenyl-4-methylimidazole, 1-benzyl-2-mercaptoimidazole, 1-benzyl-2-benzene Imidazole, 1,2-dimercaptoimidazole, 2-ethyl-4-mercaptoimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl) -2-n-undecylimidazole, 1 -(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-mercaptoimidazole, 2-phenyl-4-indenyl-5- Hydroxymercaptoimidazole, 2-phenyl-4,5-bis(hydroxyindenyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4, 5-bis[(2'-cyano) Ethoxy)indenyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole rust trimellitate, 1-(2-cyanoethyl)-2-phenyl Imidazolium trimellitate, 1-(2-oxyethyl)-2-ethyl-4-methyl succinyl trimellitic acid, 2,4-diamino-6-[ 2 '-Mercapto imidazolyl-(1,)]ethyl-s-trisyl, 2,4-diamino-6-(2'-n-undecylimidazolyl)ethyl-mestramorphine, 2, 4-Diamino-6-[ 2'-ethyl-4'-mercaptoimidazolyl-(fluorene)]ethyl--trimethylidene, 2-methylimidazole trimeric isocyanate adduct, 2 a trimeric isocyanate adduct of phenylimidazole, 2,4-diamino-6-[ 2'-nonylimidazolyl-(indenyl)ethylidene-tris-trimethylene isocyanate Further, the above-mentioned organophosphorus compound may, for example, be diphenyl, triphenylphosphine or triphenylphosphite. The above-mentioned four-stage scale salt may be mentioned. For example, there may be enumerated triphenylated gasification scales, tetra-n-butyl evolution scales, methyl triphenyl desert scales, ethyl triphenylsulfonium scales, n-butyl di-phenyl bromide scales, tetraphenyls. Brominated scale, ethyl triphenyl iodide scale, ethyl triphenyl squarate acetate, 』 』 % 〇 〇 〇 二 二 二 二 二 二 二 二 二 、 、 、 、 、 、 、 、 Three (four), tetra-n-butyl quaternary tetrafluoro side acid vinegar 'tetra-n-butyl quaternary tetraphenyl, tetra-boryl borate, etc.; The fluorene bicycloalkenene' can be exemplified by a double-production [5.4.0] undecene-7, an organic acid salt thereof or the like. Further, the above-mentioned organometallic compound ', for example, tin octylate or aluminum acetophenone conjugate can be mentioned. For example, the above-mentioned four-stage refinement can be exemplified by tetraethyl amide, tetra-n-butyl alcohol, tetraethyl hydride, tetra-n-butyl hydride, and the like. Examples of the metal toothed material include a boron compound such as tritonated boron benzene vinegar; zinc chloride or vaporized tin. .2 士高高: A point-distributed latent hardening accelerator, such as an adduct having dicyandiamide or an amine and an epoxy resin. Bovine The above:: a cystic latenthardening accelerator, for example, can be mentioned above. Meter. A latent hardening accelerator coated with a polymer such as a derivative, an organic scale compound, or a quaternary scale salt. The above-mentioned high-temperature dissociative thermal cationic polymerization type latent agent may, for example, be a Lewis acid salt or a Bronsted acid salt.匕 Promote the use of quaternary organic amine salts or quaternary four-level records. -50- 201229139 The ratio of use of the catalyst is relative to the precursor (Α,), preferably 〇.0i mass ~ Λ〇 0 shell 1 part polyorganism oxime oxygen content parts by weight ~ 20 parts by mass. In the case of the polyorganooxane precursor solvent, for example, there are some examples: Acid: A specific example of the organic solvent used in the reaction is + - Bismuth, amine, alcohol, etc. There are Ρ 鲷, f-isobutyl ketone, . Examples of the ketone' include, for example, n-n-pentanone, diethyl ketone, cyclohexanol di-diox ether, and ethylene glycol diethylene ether. Examples thereof include diethyl ether, tetrahydrofuran, and dioxane. For example, isoamyl acetate, propylene glycol monomethyl acetate, diacetic acid n-butyl vinegar, ethyl acetate, ethyl lactate, etc., and methoxy butyl acetate may be mentioned, for example, hydrazine, hydrazine. - - ψ 醯 醯 醯 Ν 醯 醯 醯 醯 曱 曱 , , , , , , , , , , 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 — — Indoleamine 7*, fluorenylamine, hydrazine, acetophenone, hydrazine, hydrazine-diethylacetamide, estrone ethyl D々 &amp; N &quot;&quot; Ν - A. ! (· acridone, Ν-methionyl porphyrin, Ν_methylmethyl pyridine, μ 7 in the gentleman 4 into the yoghurt bite, Ν-methyl hydrazinopyrrole 醯-acetyl porphyrin, Ν-Ethyl group, Ν-acetate group II ratio σ. The above alcohols may be exemplified by diol monomethyl ether, ethylene glycol monoethyl ketone mono-n-butyl ether, propylene glycol mono-n-propyl n-propyl group. Ether, etc. The proportion of the organic solvent used, - hexanol, 4-methyl-2-pentanol, ethylene glycol mono-n-propyl propyl, ethylene dipropanol monoethyl ether, propylene glycol alone in the reaction solution in the organic solvent - The ratio of the total mass of the components of 51 to 201229139 to the total amount of the reaction solution is 0.1 mass% / 〇 〜 5 5% by mass, more preferably 5% by mass to 5% by mass. Polyorgano oxetane precursor The reaction of (A') with a carboxylic acid is preferably 0 ° C to 200 ° C, more preferably 5 〇 t; 〜 15 〇 t: temperature, preferably 0.1 to 50 hours, more preferably 〇 5 hours to 2 hours. [Polyorganic compound (A") reacts with acid]

The specific slow acid 1 used in Ilia to (4) is a compound having a group containing a polymerized, fluorene double bond and a carboxyl group. The above description of the group of the polymerizable carbon-carbon double bond of the polyorganosiloxane compound (A) is the same as the case of the above-described description of the group of the carbon-carbon double bond of the polyorganosiloxane compound (A). For the specific carboxylic acid 1 used in 4, for example, (meth)acrylic acid, crotonic acid, α-ethylacrylic acid 'α-n-propyl acid, α-n-butylacrylic acid, maleic acid, fumaric acid can be used. , citraconic acid, fumaric acid, itaconic acid, etc., one or more of which may be selected in the production method 4, 'in the case of a carboxylic acid, only a specific carboxy group g or a specific carboxylic acid 1 may be used together with the above specific carboxylic acid. Acid 2, or use it together. In the present invention, a part of the specific carboxylic acid may be substituted with the compound represented by the above formula (4) insofar as the effects of the present invention are not impaired. In this case, the synthesis of the polyorganosiloxane compound (A) is carried out by reacting an epoxy group-containing polyorganosiloxane with a mixture of a specific carboxylic acid and a compound of the above formula (4). The compound represented by the above formula (4) is the same as that shown in the production method 3. In the present invention, when a specific carboxylic acid and other pretilt compound are used at the same time, it is preferred that the specific slow acid and other pretilt-developing compounds are used for carbon-based polymerization and have a propylene-based propylene group. Compound 1, we will use the ratio of the present and the present in the future -52-201229139, the ratio is better, and the more current system is better than the previous one. The ear polyorganism 矽 Λ ΠΛ ^ 1 ^ 乳 具有 具有 具有 具有 具有 具有 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 At this time, the object; π # + b hope, the total of other pretilt angles relative to the specific tickic acid, ^

In the range of 50% or less, the use rate of other pretilt angles is more than 75 m. ^ ^ 〜' may have an adverse effect on the reactivity of the liquid crystal. The suitable ratio of each of the carboxylic acids in Process 4 is such that the preferred ratios of ^ A A A are as follows. In terms of the total proportion of use of ruthenium, the phase t rA, Ma ^ is preferably an epoxy group having a molar concentration of 1 mole of organic oxime (A), preferably Αλ ^ 0 9 for κ 杈 preferably 0.1 mole to 0.9 mole Ear, 0·2 Moer~〇·7 Moar, further preferably 0.3 Mo Er~0.5 Mo Er Jia 2=Acid 1 in terms of the proportion of use, relative to the whole..., more than 50 Mohr/〇 , 〇 9. More than Mole. Κ Above, the step-by-step ratio is better for the use ratio of the acid 2, compared to the total (tetra) acid, preferably 5 moles of ί 3° mol%, and further steps in addition to the It::4 poly organic In addition to the acid reaction and the precursor of the precursor (Α) and the above-mentioned acid bypass, it can be used as the polyorganooxane precursor (Α,) and carboxylic acid in It is carried out as described in the reaction. . As described above, the polyorganic compound (4) liquid crystal alignment agent (VIII) of the present invention can be obtained, except for the above polyorgano compound-53-201229139 (A) or the like, which may contain a polyorganosiloxane compound (A). Polymer (hereinafter, referred to as "other polymer,") as [A] polymer component. [Other polymers] Other polymers can be; ^ τ ei , « Ice, horse has further improved liquid crystal alignment agent (Α) The combination, the characteristics, and the electrical characteristics of the obtained liquid crystal display element are used. In terms of the substance, the group is exemplified by a group consisting of polylysine and polyimine, and at least one selected from the group consisting of (Polymer (8)); at least one selected from the group consisting of polyorganooxane represented by the following formula (4)), a hydrolyzate thereof, and a condensate of the hydrolyzate thereof (hereinafter, also referred to as "" Phenanthracene, polyphthalate, polyester, polyamine, fibrin derivative polyacetal, polystyrene derivative, poly(styrene phenylmaleimide) derivative, poly(A) Base) acrylate and the like.

XA

I (a1)

Si — Ο

I ΥΑ In the above formula (al), hydrazine is a hydroxyl group, an alkyl group having 1 to 5 carbon atoms of a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 2 carbon atoms. Α Α is a hydroxyl group or an alkoxy group having 1 to 1 ring of carbon atoms. [Polymer] The polymer (Β) is at least one polymer selected from the group consisting of polyproline and polyimine. Hereinafter, poly-proline and polyimine will be described in detail. [Polyuric acid] Polylactoic acid is obtained by reacting four acid-lowering di-hepatic and diamine compounds to obtain -54-201229139. In the case of the tetracarboxylic dianhydride, for example, another month 3 aliphatic tetracarboxylic acid di if, lipoic tetracarboxylic acid di-needle, aromatic tetra-rebel acid _ red *--specific. These tetracarboxylic dianhydrides may be used singly or in combination of two or more. For example, tetrabutyric acid, an aliphatic tetracarboxylic dianhydride, an anhydride or the like can be mentioned. In the case of an alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid - calving is listed. - Anhydride, l, 3, 3a, 4 ' 5, 9b - hexa-5-(tetraki-2,5-dioxan3 trinyl)_cai(1) furan-1,3-dione, l ,3,3a,4,5,9b-hexahydro-8-fluorenyl_5_(tetrahydro-2 5 dioxy-3-furanyl)-naphthoquinone n,2_c]furan_l53_dioxene, 3 oxygen 1 bicyclo[3.2.1]octyl-2,4-dione-6-spiro_3'-(tetrahydro-sigma-2,5,_ _ , —* Srj ) ^ 5-(2,5-di Oxytetrahydro-3-(furanyl)_3-mercapto-3_cyclohexene], 2·dicarboxylic anhydride, 3,5,6-tricarboxy-2-indenylnorbornane_2:3,5 :6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3·3 〇]xin·2:4,6:8 dianhydride, 4,9_二玉衣[5.3.1.02勹十一_ 3,5 8,1〇·tetraketone, etc. The dianhydride: the sulphur tetracarboxylic dianhydride, for example, can be exemplified by the pyromellitic acid dianhydride, and the tetracarboxylic acid system described in the Japanese Patent Application No. 2〇1〇_97188. Among the tetradecanoic acid dianhydrides, preferred are alicyclic tetracarboxylic dianhydrides, more acidic oximes, 5.3 tris-cyclohexyl pentyl acetic dianhydride or hydrazine, 2,3,4-cyclobutane tetraindole Yixuan 'Special's 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. Tian Mi is especially 2,3,5-dicarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane tetra 1 oxime. For the use of $, it is preferably more than or equal to or less than 20% by mole based on the total of the tetracarboxylic dianhydride, and particularly preferably only 2,3 5 3 - 55 - 201229139 ridylcyclopentyl acetic acid In the case of a diamine compound, it is exemplified by an aliphatic form. In this case, the cyclic diamine, the diamine organic oxalate, and the aromatic amine compound may be used alone or in combination with two or more kinds to give an aliphatic diamine and an amine. Dimethyl hydrazine 1,3 - propylene February female, butyl diamine, - this amine - hexamethylene diamine. In the case of alicyclic diamines. 'For example, there may be mentioned 1 4_ _ &amp; alkane, 4,4,-arylene di(cyclo), monoaminocyclohexyl. Hexamethyl, hydrazine, bis(aminomethyl)cyclohexane, etc. For example, in the case of an organic 矽 % % pit, for example, 能 蛊 丙基 ) ) ) ) ) ) 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- , , There is a Japanese wish 4 - amine 0 to make a diamine diphenylmethane, hepta-4, naphthyl, 2,2'-diindenyl 4,4, bis (trifluoromethyl) Biphenyl. For example, it can be exemplified by p-diamine, 4,4, niece-phenylthio, 1,5- &amp;-amino-phenyl, 4,4'-diamino-2, 2, _, 7--amino hydrazine, 4,4'-diamine-depleted w ether, 2,2-bis[4-(4-aminophenylamino-phenyl) hydrazine, 2, 2-bis[4_(4, oxo oxime, propylene, 9,9-bis(4-aminobis(4)aminophenyl)hexa-phenyl]hexa-propionate (aniline), 4,4 ,-(Intermediate stretch/its, a 4,4-(p-phenylene diisopropanyl (4-aminophenoxy)benzene, 44,&quot;^isopropyl)-(aniline), anthracene , 4, double-loaded '(4-aminophenoxy)biphenyl, 2,6-diamino group. π疋, 3,4-diamine, its pyridine, 2,4-diaminopyrimidine, 3,6-diamino acridine, 3,6-diamine 咔 r r * w - λ. Methyl smectite-diaminocarbazole '... bis(4-aminophenyl)-biphenyl _3,6'-amino-based card. Sit, Ν, Ν, such as 'Ν, Ν'- Bis(4-Aminophenyl)_Ν,Ν,_二56- .201229139 Methyl benzidine, 1,4-bis-(4-aminophenyl)-piped, 3,5-diamino benzoin Acid, hexanyloxy-2,4-diaminobenzene, tetradecyloxy-2- 4-diaminobenzene, fifteen decyloxy-2,4-diaminobenzene, hexadecane Oxy-2,4-diamine basic, octadecyl-2,4-diaminobenzene, dodecaoxy-2,5-diaminobenzene, tetradecyloxy-2,5 -diaminobenzene, fifteen decyloxy-2,5-diamine basic, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, Bile alkoxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy -2,4-diaminobenzene, 3,5-diaminobenzoic acid choline, 3,5-diaminobenzoic acid choline, 3,5-diamine rest Aromatic acid wool, alkyl, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4-di Fluoromethoxyphenoxyoxy)cyclohexyl_3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzylidene)cyclohexyl_3,5•diamine Benzoate, 1,1-bis(4-((aminophenyl)indenyl)phenyl)-4-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl) Phenyl)_4_heptylcyclohexane, bis(4-((aminophenoxy)indolyl)phenyl)·4-heptylcyclohexane, hydrazine, hydrazine bis (4-((amino) Phenyl) indenyl)phenyl)·4_(4_heptylcyclohexyl)cyclohexane, 2,4-diamino-indole, indole-dipropylpropylaniline, 4-aminobenzylamine, 3- Aminobenzylamine and a diamine compound represented by the following formula (Α-1).

\ CtHa+i (A -1 ) J s In the above formula (A-1), 8 is a methylene group, an alkylene group having 2 or 3 carbon atoms, -〇-, -COO- or -OCO-. r is 〇 or 1. s is an integer from 0 to 2. t is an integer from 1 to 20. -57- 201229139 The ratio of use to the polyfluorene compound is more than 0.3 equivalents to 1.2 equivalents of the tetracarboxylic acid. The synthesis reaction is -20 ° C ~ 150 ° C, hours ~ 2 4 hours, j on the organic solvent solvent, no special (NMP), N,N-di-decyl imidazolidinone hexamethylenephosphonium triazine, benzene, halogenated in terms of organic solvent diamine compound chain (a + b), compared with % to 30 mass %. After the reaction, the preparation of the reagent (A) is supplied to the separation reagent of the proline acid after the purification of the liquid polyamine, and the obtained pressure-evaporating reaction solution can be enumerated as long as it is The polyamine limit which can be dissolved and synthesized, for example, may be exemplified by 1 methyl 2__methylethylamine, N,N-dimercaptocarbamide, dimercaptosulfoxide, γ-butyrolactone, and tetramethyl The tetracarboxylic dianhydride in the synthesis reaction of the basic acid and the anhydride group of the dianhydride contained in the equivalent of the equivalent of the diamine compound are 0.2 equivalents to 2, b, and are preferably in an organic solvent. get on. The reaction temperature is more preferably 〇 ° C to 100 ° C. The reaction time is preferably &amp; L is preferably from 2 hours to 12 hours. An aprotic polar solvent such as an amine; a phenolic solvent such as a phenol or a phenol. The amount of use (a) is 'relative to the amount of tetradecanoic acid (b) and the amount of the organic solvent (the t of the compound is from 0.1% by mass to 50% by mass, more preferably, the poly-branched acid solution can be used The liquid solution r' may be directly supplied to the preparation of the crystal alignment agent (A) contained in the reaction solution, or may be supplied to the preparation of the liquid crystal alignment agent (A). For example, the reaction solution is injected into the solution. a method of drying a large amount of unexhausted material under reduced pressure, a method of evaporating, etc. The method for purifying poly-proline is redissolved in the organic solvent, and the diamine amine group is preferably 0.5 acid.酉 酉 Ν Ν Ν - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - [Polyimide] hair dryer, vacuum distillation, ancient Jd4 ^, organic solvent, etc. Polymerization dehydration polyamidamine, acid structure is better for polyamido dissolved in the catalyst polyamine The ruthenium amine can be borrowed from nr: a group of lysine醯, 醯 imidization to manufacture. Polyimine can be: acid has a proline structure throughout August, p dehydration closed 醯 醯 醯 裱 也 也 也 也 也 也 也 也 也 也 也 ^ ^ ^ Partial dehydration ring closure of hydrazine, partial ruthenium imide of guanamine and ruthenium ring structure. The method of synthesizing styrene is exemplified by (i) heating 酉: (hereinafter, referred to as " Method (1)"), U〇 in a polyglycine machine solvent 'adding a dehydrating agent to the solution and dehydrating ring closure, heating according to the need (hereinafter, referred to as "method (ii)"), etc. In the method (i), the reaction temperature is preferably 5 〇. 〇~2 〇〇, 60 C to 170 C. When the reaction temperature is less than 50 ° C, the dehydration ring closure is sufficiently performed, and the reaction temperature exceeds 200. (:, the obtained knife ink of the polyimide may be lowered. As the reaction time, it is preferably 0.5 hours to 48 hours, more preferably 2 hours to 20 hours. Method (i) The amine can be directly supplied to the preparation of the liquid crystal alignment agent (A); Separating the polyimine and supplying it to the preparation of the liquid crystal alignment agent (A); or supplying the liquid crystal alignment agent (A) after refining the separated polyimine or after purifying the polyimine In the preparation of the dehydrating agent in the method (ii), for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be mentioned. -59- 201229139 As far as the amount of the dehydrating agent used is concerned, it may be desired The ruthenium imidization ratio is appropriately selected, but is preferably 0.01 mol to 20 mol with respect to the guanamine structure of the oxime polyamine. For the dehydration ring-closing catalyst in the method (11), for example Examples thereof include pyridine, triazole pyridine, dipyridyl pyridine, and triethylamine. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 mol to 1 mol with respect to 1 mol of the dehydrating agent. Further, the more the content of the above dehydrating agent and the dehydration ring-clogging agent, the higher the ruthenium iodide ratio. The organic solvent used in the method (ii) may, for example, be an organic solvent similar to the organic solvent used in the synthesis of polyamic acid, and the reaction temperature in the method (11) is preferred. Why? 〇 ~ 18 〇 it, more preferably 10 ° C ~ 150 ° c. In terms of reaction time, it is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours. When the reaction conditions are controlled within the above range, the dehydration ring-closure reaction can be sufficiently carried out, and the molecular weight of the obtained polyimine can be optimized. The method (U) gives a reaction solution containing a polyimine. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent (A), or may be supplied to the liquid crystal alignment agent (A) after the dehydration agent and the dehydration ring closure catalyst are removed from the reaction solution, or after the separation of the polyimine. Further, it is supplied to the preparation of the liquid crystal alignment agent (A), or after the separation of the separated polyimine, and then the preparation of the liquid SB alignment agent (A). The method for removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution may, for example, be a solvent replacement method or the like. The separation method and the purification method of the polyimine are, for example, the same as those listed in the separation method and the purification method of poly-proline. -60-201229139 and the like. [Other polyorganisms] The liquid crystal alignment agent (A) is also a polyorganosiloxane compound (a) in addition to the polyorganosiloxane compound (a). The other polyorganocene oxime is preferably at least one selected from the group consisting of polyorganooxane represented by the above formula (5), a hydrolyzate thereof, and a condensate of a hydrolyzate thereof. Further, when the liquid B 曰 alignment d (A) contains another polyorganosiloxane, most of the other polyorganosiloxane may be present independently of the polyorganosiloxane compound (a), or a part thereof may be The condensate of the polyorganosiloxane compound (A) is present. Examples of X1 and γΐ in the above formula (5) include: an alkyl group having 1 to 20 carbon atoms, for example, an anthracenyl group, an ethyl propylidene group, a n-butyl group, a n-pentyl group, a n-hexyl group, and a positive group. Heptyl, n-octyl:, n-decyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, positive 17:: The octadecanthyl group, the n-xyl group, the decyl group, etc.. For the alkoxy group having 1 to 16 carbon atoms, for example, there are methoxy, oxy, etc.; With respect to the aryl group having 6 to 20 carbon atoms, for example, other polyorganocenes such as a phenyl group can be exemplified, for example, by hydrolyzing red in the presence of water and a catalyst, preferably in a suitable organic solvent. &lt; A solution · condensation of at least one calcined compound of the group consisting of an alkoxylated compound and a fossilized compound (hereinafter referred to as "raw material to be synthesized. ^,} -61 - 201229139 The raw material decane compound which can be used here is t-tetramethoxy oxime, tetraethoxy decane, tetra-n-iso-isopropoxy decane, tetra-n-butoxy a non-alkoxy group such as decane, tetra-second, second butoxide, or the like; a fluorenyl tris-methyldiphenoxy oxime, etc., such as tetradoxane or decyltriethoxydecane. Methyl triaryloxy sulfonium; ethyl trimethoxy oxane such as ethyl trialkoxy permethoxy decane, phenyl triethoxy decane, etc.; Dimethyl dialkoxy decane such as methyl dimethoxy decane, Ershi Shi Xi Yuan; trimethyl phthalic trimethyl sulfoxide such as dimethyl dioxin, trimethyl ethoxy decane矽 等 etc. Among them, 'preferably tetramethoxy methoxy decane, methyl trimethoxy decane, methyl triethoxy trimethoxy decane, phenyl triethoxy oxime, dioxane, two Methyl diethoxy decane, trimethyl methoxy ethoxy decane. When synthesizing other polyorganosiloxanes, any of them can be exemplified, for example, an alcohol compound, a ketone compound, a brewing compound or other non- A protic compound. These compounds may be used singly or in combination of two or more. Examples are: monool compounds such as decyl alcohol, ethanol, n-propanol, isopropanol, n-butyl hydrazine, butanol, and third butanol; ethylene glycol, 1,2-propylene glycol, and 1,3-butanediol , pentamidine pentanediol 2,4, hexanediol-2,5, heptanediol_2,4 •, for example, fluorenyloxy oxo*, -butoxy decane decane; methyl- Alkoxydecane&gt;, methyltrilacole; phenyltrimethoxysilane; 'diethoxyethoxy' alkane; trimethyl: oxydecane; l decane, tetraethyl 4-decane, benzene' a bis-oxooxy group; a decane, a triterpene organic solvent compound or a solvate, an isobutanol, a diol-2,4,2-'2-ethylhexan-62-. 201229139 Alcohol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyvalent alcohol compounds; ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Alcohol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylene diether ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol single Propyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monoterpene ether, C Partial ethers of polyhydric alcohol such compounds glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether Yue, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether and the like. Examples of the ketone compound include monoketone compounds such as acetone, methyl ethyl ketone, methyl-n-propanone, and decyl-n-butanone; acetamidine acetone, 2,4-hexanedione, and 2,4-heptanedione. And a 0-diketone compound such as 3,5-heptanedione or 2,4-octanedione. Examples of the above guanamine compound include decylamine, N-mercaptodecylamine, hydrazine, decyl-didecyl decylamine, acetamide, N-methylacetamide, hydrazine, hydrazine. - dimethyl acetamide, hydrazine-ethyl acetamide, hydrazine, hydrazine-diethyl acetamide, hydrazine-hydrazinopyrrolidinium, hydrazine-ethenyl porphyrin, hydrazine-ethinylpiperidine , Ν-acetylpyrrolidine and the like. Examples of the self-acting compound include diethyl carbonate, carbonic acid vinyl ester, propylene carbonate, diethyl carbonate, decyl carbonate, ethyl acetate, γ-butyrolactone, and γ-valerolactone. , n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxy butyl acetate, cesium acetate Amyl pentyl ester, 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, decyl cyclohexyl acetate, n-decyl acetate, decyl acetate, -63- Ethyl acetate, ethyl acetate, tm, acetic acid, diethylene b-alcohol, early formazan, B &amp; early methyl ether, rm ethylene glycol, monoethylene glycol, mono-n-butyl, acetic acid, diethyl hydrazine 7 ^ „ 鲥, 醆 醆 醆 - 醆 „ 一 皂 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Ethyl ether, ethyl propylene glycol monoacetate dipropylene-age DD ether, acetic acid methoxy triethyl _ 知早乙鳞, di-propane shovel per ester ester, internal acid acetamidine , Ethyl pentoxide, Diethyl hydrazine, n-butyl propionate, 酉 酉, lactic acid n-butyl gt ^, di-n-butyl oxalate, lactic acid propionate, di- lactic acid, valerate, lactic acid B-methyl ester, t-acid diethylene phthalate, ortho-benzoquinone other aprotic θ 4 . I Keya hard, Ν, Ν, Ν, Ν, · four °, for example, can be listed as acetonitrile, -1 amine, heart methyl (10) sulfonamide, hexamethyl | ° ratio ° Lin, N-A Mei Guang base%. Each, heart ethyl.嘻,嘻甲Α χτ methyl piperidine, Ν7 甘土 G Ν-methyl-Δ3- 'methyl propyl mouth, Ν _ methyl ^ bottom. Ding, Ν, Ν-dimethyl mother listening, methyl ~ ~, UV (9), small methyl 2 _ ..., Ν _ four gas < (1 mouth. Ding _ et al. base ~ 2 'weivalin, 1, 3-Dimercapto', part of the polyol compound:: Solvent: 'Specially for the synthesis of polyols to synthesize other poly-right oxime. Or bismuth compound. = In the case of raw material pulverized compound:: In the hospital, the amount of water used Words, phases, ears, preferably 〇·〇丨草和, alkoxy and halogen atoms, the total amount of 1 ear, into - cattle $, ~ 100 moles, more preferably 0.1 moles ~ 3 〇 Mo progress More preferably, it is 1 mole of M bucket 30, and::&gt; 耳耳. For example, At ° is used as a catalyst for other polyorganisms. * 1 J can be listed as metal chelated 铋 (4) , ammonia, 蝥σ, organic acid, inorganic acid, organic alkali metal compound, etc.. For the above metal chelate, 5 ' can be exemplified by triethoxy · -64 - 201229139 mono (acetylpyruvate)鈇等二. One seek-tomb; milk base • early (ethyl pyruvate) titanium; diethoxy bis (acetyl acetonate) titanium and other dialkoxy • bis (acetyl acetonate) titanium • ginseng (acetonitrile pyruvate) titanium and other monoalkoxy • ginseng (acetonitrile, ruthenium, titanium, ruthenium, acetophenone, acid, titanium, triethoxy, mono (ethyl acetoacetate), titanium, etc. Oxy. mono(ethylacetamidineacetic acid) titanium; ethoxylated bis(ethylacetamidineacetic acid) titanium #二烧氧•double (B&amp;ethyl acetate); monoethoxyl (Ethylacetamidineacetic acid) monoalkoxy such as titanium, hexanylacetate, titanium, acetoacetate Titanium chelate such as titanium compound containing chelating ligand, such as bis(ethylpyruvylacetate) bis(ethylacetamidineacetic acid) titanium, ginseng (acetamidine s oxime) mono(ethylacetamidineacetic acid) titanium a trialkoxy-mono(ethylpyruvylpyruvate) oxime, such as a trialkoxy, a mono(acetonitrile oxime) oxime, an ethoxy group, a bis(ethyl acetopropionate) oxime, etc. • double (ethyl acetonitrile) acid; monoethoxy • ginseng (ethyl propylene (iv)) wrong mono-alkoxy • tris(acetyl ketone) lanthanum; cerium (acetyl acetonate) zirconium; Ethoxy/mono (ethyl acetoacetate), etc., three alkoxy groups. Single (B) Acetylacetate) 1 ethoxylated acetic acid m, etc., di-oxygenated oxy, bis(ethyl ethanoacetic acid), syl ethoxy, ginseng (ethyl ethanoacetic acid), etc. (ethyl acetoacetate) wrong; 肆 (ethyl acetonitrile acetic acid) wrong; single (acetyl acetonate) ginseng (ethyl ethyl styrene acetate) wrong, bis (ethyl acetoacetate) bis (ethyl acetamidine) Acetic acid), ginseng (acetyl acetonate) mono (ethyl acetoacetate) hydrazine and other two or more compounds containing chelating ligands, such as chelating ligands; ginseng (pyruvate); Ethyl ethyl styrene acetate, etc. (tetra), etc. For the above organic acid, for example, formic acid, acetic acid, C-65 - 201229139 酉 4 aliphatic saturated carboxylic acid; malonic acid, &amp; · k^ Tian Ma酉 owed to the special aliphatic unsaturated carboxy oxime, salicylic acid, benzoic acid, neighboring stupid two #甲笑石生缺w * 放雄- τ 0 Yisi Fangxiang carboxylic acid; 曱 ... acid The fragrant family continues to acid; single... = acid and so on... slow acid; drop acid, tartaric acid, etc. - gas acetic acid hydrofluoric acid, phosphoric acid, etc. There are - red, nitric acid, sulfur. For the above organic base, for example, hydrazine. Billion. 、,...曱...,° ratio... Alcoholamine, Diethanolamine, Dimercaptomonoethanolamine, A: Ethylamine, Monoethyltriethanolamine, Dioxetane, Early Methyldiethanolamine, Monocarbene, IV Methyl chloride hydroxide ^bicyclic two.丫双环十 In the above-mentioned alkali metal compound, potassium hydroxide, cesium hydroxide, and ruthenium hydroxide are exemplified by sodium hydroxide alone or in combination of two or more. These catalysts can be used in the presence of these catalysts, preferably in the case of gold metal chelates, in which the amount of a, organic, and inorganic A&amp;JL·4 is equivalent to that of the catalyst. Preferably, it is 0.001 parts by mass of the oxime denier, and the raw material decane compound is part by mass. Berry's 'better for 〇·〇〇】Quality ~! The catalyst may be preliminarily added to the solvent: dissolved in the compound::: or in the organically added water. , 尹 尹 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或Dissolved in -66 - 201229139 in organic solvents. The reaction temperature at the time of synthesizing other polyorganodecane is preferably 〇c~loo c, more preferably 15t&gt;8 (rc. The reaction time is preferably 〇"~24 hours" more preferably 1 hour~8 When the liquid crystal alignment agent (A) contains the polyorganosiloxane compound (A) and other polymers, the amount of the other polymer is relative to 1 part by mass of the polyorganosiloxane compound (A). It is preferably 10,000 parts by mass or less. The content of the KS is more preferably different depending on the type of other polymers. The liquid aa alignment agent (A) contains a polyorgano oxy-oxygen compound (A) and a polymerization 1 (B)犄, as a preferred ratio of use of the two, the total amount of the polymer (B) is preferably 1 〇〇 里 〜 5,000 5,000 parts by mass relative to 100 parts by mass of the poly- oxane compound (A). More preferably, it is 200 parts by mass to 3,000 parts by mass. In addition, the liquid crystal alignment agent (A) contains a polyorganosiloxane compound (), and the preferred ratio of the two is used when the organic solvent is used. 5 times as the other polyoxyxane relative to the polyorganosiloxane compound (A) Parts to 2 parts by mass, preferably (7) parts by mass to 2 parts by mass. The liquid crystal alignment agent (A) contains a polyorganosiloxane compound (A) and other materials as other polymers. It is preferably a polymer (β) or another polyorganosiloxane. <Other components>, a liquid crystal alignment agent (Α) may also have a hardener or a hardening catalyst within a range not impairing the effects of the present invention. And a hardening accelerator, at least one ring gas in the molecule, a compound of the latex (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, etc. , hardening catalyst and hardening accelerator] -67- XT ) Υ 201229139 The curing agent and the hardening agent may be included in the liquid crystal in order to make the crosslinking reaction of the polyorganooxygen (A) stronger. The hardening accelerator may be included in the liquid crystal alignment agent (A) for the hardening reaction of you, &amp; As the hardener, a hardener which is usually used as a hardenable material having an epoxy group or a hardening composition containing an epoxy group. For the shaft and the yut-like hardener, for example, there are oxime amine, polycarboxylic acid hydrazine, and polybasic citric acid. In the case of a polyvalent carboxylic acid anhydride, t'At is known as Cyclohexane III and other polybasic slow anhydrides. In the case of cyclohexane tricarboxylate __ q • phthalic anhydride, for example, decanoic acid-3 hexanyl 12λ ' —, cyclohexane. US-tricarboxylic acid-3,5 ,4 ψ A can be cited. _, _ anhydride, etc. In the synthesis of other polycarboxylic acids such as 4-methyltetrahydroortho- _, _ ling net phthalic anhydride, methyl norbornic acid diacid, trimellitic anhydride, lower: two: maleic acid &quot; The compound of the field, the poly- τ tong; the _ used by the _ 罗 罗 稀 稀 妓 妓 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外 此外The reaction products of hydrazine and their hydrogenated products and the like. (6) The above formula (6) φ X is an integer of 1 to 20. For example, the hexafluoride hydrate compound can be exemplified as a hardening sputum, and the carboxylic acid anhydride cyclohexane-anhydride and cyclamate can be exemplified. Amino acid oil thin, anhydride diide, -68-201229139, fluorinated disc 5, diethylpyruvate aluminum, and the like. These catalysts may be cationically polymerized by heating a catalytic epoxy group. Examples of the hardening accelerator include, for example, an imidazole compound, a 'quaternary scaly compound, a quaternary amine compound, and a di-sigma-bicyclo[5-ported] deca-carbene-7 or an organic acid salt thereof. Bicycloolefin; octanoic acid, octanoic acid:: Shao:: organometallic compound such as C-compound; three said oxidized, base phase compound; zinc chloride, tin chloride and other metals "material bismuth (tetra), amine and epoxy Resin adducts and other amine-added pro-melting-point-dispersion latent hardening accelerators; quaternary scale salts, etc.: microcapsule-type potentials covered by compound Α hardening accelerator: salt type potential integration!, Louis A thermal cationic polymerization type latent curing accelerator such as an acid salt or a cloth succinate. [Epoxy compound] A liquid crystal alignment film formed from k 对 can be bonded to the surface of the substrate by right 乂曰 amp amp Sexual considerations 丄=Night day aligning agent (A) contains the above epoxy compound. For the oxime compound, 'preferably 乙二_, polyethyl-c S to a glycidyl ether group g-alcohol condensed water Glyceryl ether, tripropyl hydrazine ^ % - glyceryl ether, new pentylene _ Glycidyl ether, glycerol:::: glycerol-based mystery, A-hexane diol diglycidyl primordial scale, "diglyceryl ether, 2,2·di-dixindiol diglycidyl, 3, 5,6-tetraglycidyl · 2,4_hexamethylene sulphate, 丄 ^ ^ , Ν ', Ν '_ &amp; glyceryl _ m-dioxane diamine, _ amine A, m and shrink Glycerin base)% hexane, hydrazine, hydrazine, hydrazine, hydrazine, quaternary, quaternary, glutinous, glutinous, quaternary, quaternary, quaternary - Benzylamine, oily odor lower amine N, N-di-condensed oil oleyl decyl cyclohexane. 1 π -69- 201229139 When the liquid crystal alignment agent (A) contains an epoxy compound, its content ratio is relative to the above The mass ratio of the polyorganosiloxane compound and the other poly-5 compound to be used is preferably from 0.1 part by mass to more than 0.1 part by mass. When the liquid crystal alignment agent (A) contains an epoxy compound, a base catalyst such as 丨-benzylmethylimidazole may be used in combination in order to make the crosslinking reaction more efficient. [Functional decane compound] A functional decane compound may be used. In order to improve the adhesion of the obtained liquid crystal alignment film to a substrate, the functional decane compound may, for example, be 3-aminopropyltrimethoxydecane or 3-aminopropyltriethoxydecane. 2-Aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2- Aminoethyl)_3_aminopropylmethyldimethoxycarbazide, %ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxylate, N-ethoxylated group 3-aminopropyltrimethoxy decane, N_ethoxycarbonyl-3-I-propylpropyldiethoxy decane, N-triethoxycarbamidopropyltriethylenediamine, N -trimethoxysulfonylpropyltriethylenetriamine, 1〇·trisyloxymethylcarbazide_1,4,7-triazaindene, ι〇_triethoxyphthalide Xi Xuanji-1,4,7-triazadecane, 9-trimethoxycarbamimidyl-3,6-diazepine acetate, 9-triethoxycarbamido-3, 6-diazepine 6 acid ester, N-nodal-3-aminopropyl trimethoxy decane, N-based -3-3 aminopropyl diethoxy Alkane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, 1 bis(oxyethylene)_3•aminopropyltrimethoxy Base decane, bismuth(bis)(oxyethylene)_3_aminopropyltriethyl-70-201229139 oxy, 3-glycidoxypropyltrimethoxydecane, 4 cyclohexyl)ethyltrimethoxy Decane, etc.

And the tetracarboxylic dianhydride described in Japanese Laid-Open Patent Publication No. B7J63-291922, and the like. A reactant of an alkane compound or the like. * When the liquid crystal alignment agent (4) of the earth contains a functional ceramsite compound, the ratio of 1 is contained in relation to the above [A] polyorgano oxy-oxygen compound and any use: 100 parts by mass of other polymers in total, Preferably 'more preferably 2. The mass part w is preferably 5 parts by mass or less, and [surfactant] is a surfactant, an anionic surfactant, a cation active agent, a polyoxymethane interfacial surfactant, or a fluorine-containing surfactant, in terms of a surfactant. For example, a nonionic interfacial active ionic surfactant, an amphoteric interfacial agent, a polyalkylene oxide surfactant, and when the liquid crystal alignment agent (A) contains a surfactant, the content ratio thereof is relative to 100 negative parts of the liquid crystal alignment agent. (A) All, preferably 1 part by mass or less 'more preferably 1 part by mass or less. &lt;Production Method of Liquid Crystal Aligning Agent (A)&gt; The liquid crystal alignment agent (A) contains the [A] polymer component as an essential component as described above, and may contain other optional components as necessary, but preferably each component A solution-like composition prepared by dissolving in an organic solvent. In the case of the organic solvent for preparing the liquid crystal alignment agent (A) in the month b, it is preferred that the [A] polymer component and any other components used arbitrarily, but not reacted with -. The organic solvent which can be suitably used in the liquid crystal alignment agent (A) is known to vary depending on the type of other polymer to be added. When the liquid crystal alignment agent (A) contains the [A] polymer component and the polymer (B) -71 - 201229139, preferred organic solvents include organic solvents as listed above for use as a human acid. . In this case, as the organic solvent to be used for the synthesis of the polyamic acid of the present invention, it may be used singly or in combination of two or more. On the other hand, when the [A] polymer of the liquid crystal alignment agent (A) has a polyorganosiloxane compound (A), or a polyorganoquinone (A) and other polyorganosiloxane, it is preferred. Examples of the organic solvent include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene, dipropylene glycol diethyl ether, dipropylene glycol propyl ether, dipropylene glycol. Didiol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, butyl ether (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol monoethylene glycol, methyl cellosolve acetic acid Ester, ethyl cellosolve acetate cellosolve acetate, butyl cellosolve acetate, decyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, acetic acid N-butyl, isobutyl acetate, n-amyl acetate, acetic acid, second amyl acetate, 3-methoxyoxybutyric acid methyl amyl acetate, 2-ethylbutyl acetate, 2-ethyl acetate Hexyl ester, n-hexyl acetate, cyclohexyl acetate, citric acid acetate, isoamyl acetate, and the like. Among them, 'preferably, n-propyl acetate, ester, n-butyl acetate', isobutyl acetate, dibutyl acetate, acetic acid, and acetic acid are used. In the preparation of the liquid crystal alignment agent (A), it is suitable to use it without using other polymers and types thereof, and it may be obtained by combining one or more of the above. Such a solvent is preferably a polyglycol which can be used in combination with a solvent. This component contains only oxygenated compounds, such as propylene glycol monoglycol oxime oxime, ethylene glycol alone, monoester, propyl alcohol, ethyl ester, butyl acetate, ethyl acetate, acetic acid, benzyl acetate. The acid amyl acetate and the acetic acid isopropionic acid positive agent are not analyzed in the liquid crystal alignment agent (A) according to the solid content of the organic solvent-72-201229139, and the surface tension of the liquid crystal alignment agent (A) is caused. A solvent in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent (A), that is, the ratio of the mass of all the components other than the solvent in the liquid crystal alignment agent (A) to the total mass of the liquid crystal alignment agent is selected in consideration of viscosity, volatility, etc., and is preferably 1 mass. The range of mass %. The liquid crystal alignment agent (A) is applied onto the surface of the substrate to form a coating film composed of a liquid crystal alignment film. However, when the solid content concentration is 1% by mass or more, the film thickness of the coating film does not become too small, and a good liquid crystal alignment can be obtained. membrane. On the other hand, when the solid content concentration is 1% by mass or less, it is possible to obtain a good liquid crystal alignment film which suppresses the film thickness of the coating film from being excessively large, and also prevents the viscosity of the liquid crystal alignment agent (Α) from increasing. , good coating properties are obtained. The range of the particularly preferable solid content concentration differs depending on the method employed in coating the liquid crystal alignment agent on the substrate. For example, the spin coating method is particularly preferably in the range of 1.5% by mass to 4.5% by mass. In the case of the printing method, the solid content: the agricultural degree is controlled in the range of 3 mass% to 9 mass%, and thus the solution viscosity: mPa.s to 5 〇 mPa.s is particularly preferable. In the case of the inkjet method, the solid: component concentration is controlled in the range of 丄 mass% to 5% by mass, and the range of 3 mPa.s to 15 mPa.s is especially * Λ Λ N ni , , 丨 〜 I The temperature of the liquid crystal alignment agent T is preferably (TC~2〇(TC, more preferably 〇t~4〇). [Embodiment] Hereinafter, the implementation of the present invention is not limited to the following embodiments of the present invention. The obtained weight of the gas having the ring gas and (8) the polyorgano compound is determined by the GPC method of the following method. The polystyrene-converted &lt;-straight-battery-73-201229139 column: manufactured by TOSOH Co., Ltd., TSKgelGRCXUl solvent: tetrahydrofuran Temperature: 4 CTC Pressure: 68 kgf/cm 2 In addition, the amount of the raw material compound and the polymer used in the following examples is ensured to be able to repeat the synthesis of the raw material compound and the polymer at the synthetic scale shown in the following synthesis examples as needed. Synthesis of specific carboxylic acid &gt; [Synthesis of specific carboxylic acid 1] The specific acid 1 was synthesized according to the following reaction route.

COOMe

0(ch2)1〇cooh K2CO3

DMF

LiOH H20 MeOH / H20

NC

Specific carboxylic acid 1 [Synthesis Example 1] In a 500 mL three-necked flask equipped with a condenser, 4 cyano-4, _ phenyl benzoquinone 6 · 3 g, 1 1 - methyl bromide methyl ester 1 〇 g, potassium carbonate was added. 1 4.2 g, Ν, Ν-dimethylformamide 2〇〇mL' was heated and mixed at 16QC for 5 hours. After termination of the reaction with tlC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water 'mixed and stirred. The precipitated white solid was filtered and washed with water. The obtained solid was dried under vacuum at 8 ° C to give a compound (1). [Synthesis Example 2] Next, in a 200 mL three-necked flask equipped with a condenser, 1 g of compound 1, lithium hydroxide, monohydrate j 6 g, methanol 3 mL, and water UmL were added, and the mixture was heated and stirred at 8 ° C. 4 hours. After confirming the termination of the reaction by TLC, the reaction mixture was cooled to room temperature. While the reaction solution was under stirring, dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed successively with water and ethanol. The obtained solid was vacuum dried under the war to obtain 8 g of a special [Synthesis of a specific carboxylic acid 2]. Synthesis of a specific carboxylic acid 2 according to the following reaction route

〇(CH2)2〇H compound 2 ci c'-〇-r

Et3N ch2ci2

Cl COOMe, &lt;y

K2CO3 DMF

〇(ch2)2〇 Compound 4 COOMe

LiOH H20 MeOH/THF/H20

〇 (called 2〇 ·~〇~· Specific slow acid 2

COOH Example 3] Adding 4-cyano-4 to the head flask

500mL -75- 201229139 hydroxybiphenyl with condensation tube, 5 3 5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (tb ab), 300 mL of N,N-didecyl decylamine The mixture was heated and mixed at 1 50 ° 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 separated and washed with a mixed solution of ethyl acetate 300 ml, 1N-aqueous sodium hydroxide solution 1 〇 〇 m [. After taking the organic layer, the liquid was separated and washed with 100 N of 1 N aqueous sodium hydroxide solution and 100 mL of water. The organic layer was dried over magnesium sulfate and the organic solvent was distilled off. After drying the obtained solid in vacuo, it was recrystallized from ethanol (1 mL) / hexane (250 mL) to obtain i3.1 g of compound 2 合成 [Synthesis Example 4] 12 g of compound 2 was added to a 200 mL three-necked flask equipped with a condenser and a dropping funnel. 12.7g of 4-chlorobenzene continued helium, 60mL of dehydrated two gas, and mixed. While cooling the reaction solution with an ice bath, a solution of 6.6 g of triethylamine in dehydrated dioxane (1 OmL) was added dropwise over 10 minutes. Stir in the ice bath for 30 minutes, return to room temperature and stir for another 6 hours. The reaction solution was added with chloroform (150 mL), and the liquid was separated and washed four times with 1 〇 〇 mL of water. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was evaporated. The solid obtained was washed with ethanol to obtain 16.1 g of Compound 3. [Synthesis Example 5] In a 300 mL three-necked flask equipped with a condenser, 15 g of compound 3, methyl 4-hydroxybenzoate 1 1 g, potassium carbonate 1 2 · 5 g, N,N-dimethylguanamine were added. 1 80 mL, and the mixture was heated and stirred 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 was poured into 500 mL of water and mixed for mixing. The precipitated white solid was filtered and washed with acetic acid. The obtained solid was vacuum dried at 80 ° C to obtain 10 g of compound -76-.201229139 4 〇 [Synthesis Example 6]

In a l〇〇mL three-headed flask equipped with a condenser, 9 5 g of compound 4 虱 lithium oxide, 1-6 g of monohydrate, 3 mL of methanol, 15 mL of tetrahydrofuran, and 15 mL of water were added, and the mixture was heated and stirred at 80 ° C. The reaction solution was cooled to room temperature, and slowly added dropwise to the reaction solution was washed successively with water and ethanol. Obtained 9 g of the specific carboxylic acid 2. 4 hours. The end of the reaction was confirmed by TLC. The reaction solution was stirred to dilute hydrochloric acid. The solid which precipitated the precipitated solid was vacuum dried at 8 (TC) to give a specific tannic acid 3.

Synthesis of carboxylic acid 3] According to the following reaction route K2CO3

DMF

LiOH H20

MeOH / H2〇

Specific carboxylic acid 3 -77 - 201229139 [Synthesis Example 7] In Synthesis Example 1, instead of 4-cyano-4'-hydroxybiphenyl, 10.7 g of 2, 3, 5, 6-tetrafluoro-4-(pentafluoro) was used. Phenyl)phenol, 13.7 g of Compound 5 was obtained [Synthesis Example 8] In Synthesis Example 2, 13.5 g of Compound 5 was used instead of Compound 1, to obtain 11.2 g of a specific carboxylic acid 3. [Synthesis of Specific Carboxylic Acid 4] The specific carboxylic acid 4 was synthesized according to the following reaction route.

Specific carboxylic acid 4-78-201229139 [Synthesis Example 9] In Synthesis Example 3, instead of 4-cyano-4,-hydroxybiphenyl, 25.5 g of 2,3,5,6-tetra-I-4-(pentafluoro) was used. Phenyl)phenol gave 23 lg of compound 6. [Synthesis Example 1 〇] In Synthesis Example 4, instead of Compound 2, 1 8.9 g of Compound 6 was used to obtain 2 4.1 g of Compound 7. [Synthesis Example 1 1], using 20 g of the compound 7, it was found that in the synthesis example 5, instead of the compound 3, 1 5 · 4 g of the compound 8 was used. [Synthesis Example 12] Using 13 g of Compound 8, it was found that in Synthesis Example 6, instead of Compound 4, 1 1.4 g of the specific carboxylic acid 4 was used. [Synthesis of specific carboxylic acid 5]

MeOH / H20

[Synthesis Example 1 3] Specific carboxylic acid 5 Synthesis 15 g The number of the fluorene group was changed from 1 一样 to the specific acid 1 of the specific acid 1 and the specific enemy acid 5 was changed to 5 . -79- 201229139 [Synthesis of specific carboxylic acid 6] Synthesis of specific acid by the following reaction

FFFF specific carboxylic acid 6 [Synthesis Example 14] In a 500 mL three-necked flask equipped with a condenser, 2,2',3,3,-tetraki-4'-propyl-4-alkyl-based lO.lg was added. 11-glucuronate vinegar i〇g, potassium carbonate 14.2 g, N,N-didecylguanamine 200 mL, and the mixture was heated and stirred at 16 CTC 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 stirred. The precipitated white solid was filtered and washed again with water. The solid obtained was vacuum dried at 80 ° C to obtain 10.8 g of Compound 9. [Synthesis Example 1 5] Next, in a 200 mL three-necked flask equipped with a condenser, 10 g of compound 9, lithium hydroxide monohydrate 1.6 g, decyl alcohol 3 〇 mL, and water i5 mL were heated and stirred at 8 CTC. 4 hours. After confirming the termination of the reaction by TLC, the reaction solution of -80 - 201229139 was cooled to room temperature. While the reaction solution was under stirring, dilute hydrochloric acid was slowly added dropwise to the reaction solution t. The precipitated solid was filtered, and washed with water and ethanol in turn to obtain a solid at 8 Torr. Under vacuum, it was dried under vacuum to obtain 6 g of the specific carboxylic acid 6. [Synthesis of Specific Carboxylic Acid 7] The specific carboxylic acid 7 was synthesized according to the following reaction route.

Br-(CH2^-C〇OMe K2C03

DMF

Specific carboxylic acid 7 [Synthesis Example 16] except that the starting compound (2, 2, 3, 3, -tetrafluoro-4, -propyl-4-hydroxyl) was converted into the above reaction route. In addition to the 9.1 g compound (2,3-difluoropropyl-3⁄4 hexyl) phenol described in the above, the synthetic water of the above specific carboxylic acid hydrazine is required to be 5 · 9 g of a specific tick acid 7 . [Synthesis of a specific carboxylic acid 8] According to the following reaction path handle, human, root micro ^ synthesis of a specific carboxylic acid 8. 201229139

[Synthesis Example 17] except that 10 g of the starting compound (2,2',3,3,-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was changed to 12.9 g of the compound described in the above reaction route. In the same manner as the synthesis of the above specific carboxylic acid 6, except for (2,2',3,3'-tetrafluoro-4-propyl-4''-hydroxybitriphenyl), 7.1 g of the specific carboxylic acid 8 was obtained. [Synthesis of Specific Carboxylic Acid 9] A specific carboxylic acid 9 was synthesized according to the following reaction route. -82- 201229139 c3h7

F

+ Br-fcH〇i-COOMe \ /10

K2C〇3 -^ DMF c3h7

LiOH_H20 -► MeOH/H20 C3H7

0-^-CH2j-C00H Specific carboxylic acid 9 [Synthesis Example 18] In addition to the starting compound of lO.lg (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) In addition to 10.2 g of the compound (2,3-difluoro-4-(4-propylcyclohexylmethoxy)phenol) described in the above reaction route, 6.5 g of specific Wei was obtained in the same manner as the synthesis of the above specific tickic acid 6 Acid 9. [Synthesis of Specific Carboxylic Acid 10] A specific carboxylic acid 10 was synthesized according to the following reaction route. -83- 201229139

Specific carboxylic acid 1 ο [Synthesis Example 19] except that 10.lg of the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was changed to the above reaction route In the same manner as the above-mentioned specific carboxylic acid 6 except for the above-described synthesis of 12.6 g of the compound (2,3-dioxa-4'-(4-propylphenylethyl)biphenyl), 7.2 g of the specific carboxylic acid 10 was obtained. [Synthesis of Specific Carboxylic Acid 11] A specific carboxylic acid 11 was synthesized according to the following reaction route. -84- 201229139

ϋ0Η·Η20

Me0H/H20 [Synthesis Example 20] except that 10.lg of the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was changed to the above-described reaction route In addition to the synthesis of 1 4.2 g of the compound, 7.6 g of the specific carboxylic acid 11 was obtained in the same manner as the synthesis of the above specific carboxylic acid 6. [Synthesis of Specific Carboxylic Acid 12] A specific carboxylic acid 1 2 was synthesized according to the following reaction route. -85- 201229139

Οοη·η2ο Me0H/H2O

〇~Ci〇H2〇COOH specific retardation 1 2 [Synthesis Example 21] In a 500 mL three-necked flask equipped with a condenser, 4-[difluoro(4-pentylcyclohexyl)decyloxy]_2,3_ was added. Difluorophenol 12.5g, 11-bromoundecanoic acid 曱 10g, potassium carbonate! 4 mL of 2,2 g of N,N-dimercaptocarhamamine was heated and stirred 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 stirred. 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 22]

Next, 10 g of Compound 10, Hydrazine monohydrate l_6 g, sterol 30 mL, and water 15 mL -86 * 201229139 ' were placed in a 200 mL three-necked flask equipped with a condenser tube and heated and mixed at 80 ° C for 4 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. While the reaction solution was under stirring, dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed successively with water and ethanol. The solid obtained was dried under vacuum at 8 (TC) to give 6 g of a specific carboxylic acid 1 2 &lt;Synthesis of polyorganooxy oxane (polyorganooxane precursor) having an epoxy group &gt; [hydrolysis condensation reaction] [ Synthesis Example S-1] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 2-(3,4-epoxycyclohexyl)ethyltrimethoxylate was added (ECETS) L〇〇.〇g, mercaptoisobutyl ketone 5〇〇g and triethylamine 1〇〇§, mixed at room temperature. Then, using a dropping funnel, add deionized water l〇〇g for 30 minutes. Thereafter, the mixture was reacted under reflux for 6 hours under reflux. After the completion of the reaction, the organic layer was extracted and washed with a 2% by mass aqueous solution of ammonium nitrate until the washed water was neutral, and then distilled under reduced pressure. Solvent and water, an epoxy group-containing polyorganooxane S-1 was obtained as a viscous transparent liquid.

For the polyorganosiloxane having an epoxy group, iH_NMR analysis was carried out, and a peak derived from an epoxy group having a theoretical strength was obtained in the vicinity of a chemical shift (δ) = 3 2 ppm, and it was confirmed that no side reaction of the epoxy group was caused in the reaction. . The polyorganosiloxane (Sw) having an epoxy group having a weight average molecular weight (Mw) of Mw = 2, 2 Å and an epoxy equivalent of 186 g/mole. [Synthesis Example S-2], in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 2_(3,4_epoxy-87-201229139) was added as a hydrolyzable compound. Ethyl trimethoxy decane (ECETS) 73.9 g and γ-methyl propylene West &amp; oxypropyltrimethoxy oxalate (GMPTS) 24.8 g (ECETS: GMPTS = 75: 25 (Morbi) )) and 500 g of mercaptoisobutyl ketone as a solvent and triethylamine 10 g as a catalyst were mixed at room temperature. Then, 100 g of deionized water was added dropwise thereto over 3 minutes using a dropping funnel, and then reacted at 8 °t for 6 hours while stirring under reflux. After the completion of the reaction, the organic layer was extracted 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 a viscous transparent liquid having an epoxy group. . The hydrolyzed condensate was analyzed by ih_nmr, and a peak derived from an epoxy group having a theoretical strength was obtained in the vicinity of the chemical shift (δ) = 3.2ρρηη, and it was confirmed that no side reaction of the epoxy group was caused in the reaction. The polyorganodecane S-2 having an epoxy group obtained therein has a weight average molecular weight (Mw) of Mw = 2, 9 Å. [Synthesis Example S-3] 'In the reaction vessel equipped with a stirrer' thermometer, a dropping funnel and a reflux condenser, 2 (3,4-epoxycyclohexyl)ethyltrioxane as a hydrolyzable decane compound was added. Hydrazine (ECETS) 123 & and γ-mercaptopropene ethoxypropyl trimethoxy oxime (GMPTS) 124.2 g (ECETS: GMPTS = 5 〇: 5 〇 (mole ratio)) and: solvent 1250 g of mercapto isobutyl ketone and triethylamine 25' as a catalyst were combined under the shirt. Then, after removing 25 liters of deionized water through a dropping funnel over 45 minutes, it was stirred at reflux for 8 Torr. The reaction was carried out for 6 hours. After the reaction is completed, the organic layer is extracted, and the main layer is washed with G.2f-% nitrate in water until the water after washing is neutral. After the solvent: water is obtained under reduced pressure, a hydrolyzed condensate having an epoxy group is obtained. Viscous transparent liquid-88-201229139 The iH-NMR analysis of the hydrolysis condensate gave a peak derived from the epoxy group with a theoretical strength in the vicinity of the chemical shift (δ)=3·2ρρϊη, confirming that no epoxy was caused in the reaction. The side reaction of the base. The weight average molecular weight (Mw) of the polyorganooxime S-3 having an epoxy group obtained therein is Mw = 3,200 〇 [Synthesis Example S-4] equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS) 88 7§ and hydrazine methacryloxypropyltrimethoxydecane as hydrolyzable decane compounds were added to the reaction vessel. ^MPTS) 9.93g (ECETS: GMPTS = 9〇: 1〇 (mole ratio)) and 〇〇 异 异 异 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 mixing. Then, I00 g of deionized water was added dropwise thereto over 3 minutes using a dropping funnel, and the mixture was reacted at 80 for 6 hours while stirring under reflux. After the reaction, the organic layer was extracted with a 2% by mass aqueous solution of ammonium nitrate until the water after washing was neutral, and the solvent and water were distilled off under reduced pressure to obtain a hydrolyzed condensate having an epoxy group. Viscous transparent liquid s. The hydrolyzed condensate was analyzed by ih_nmr, and an epoxy group having a theoretical strength was obtained in the vicinity of a chemical shift of 3.2 ppm, and it was confirmed that the reaction did not cause a side reaction of an epoxy group. The polyorganosiloxane S-4 having an epoxy group obtained therein has a weight average molecular weight (Mw) of Mw = 2,7 Å. &lt;Synthesis of polyorganosiloxane compound (A)&gt; [Synthesis Example A-1] Into a 100 mL-neck flask, the 9-epoxy group-organized polyorganisms obtained in the above Synthesis Example s_i were added, 5-oxo-oxygen represented by the formula (5-5) which is one of the compounds of the above-mentioned formula (5) 3.3 g of chloric acid (pretilt component l) and 0.20 g of UCAT 18X (quaternary amine salt of San-apro Co., Ltd.) were stirred at 80 ° C for 12 hours. After the completion of the reaction, reprecipitation was carried out with methanol. The precipitate was dissolved in ethyl acetate to obtain a solution. After washing the solution three times, the solvent was distilled off to obtain i4.5 g of a polyorganosiloxane compound A-1. White powder. The VIw of the polyorganosiloxane compound A-1 is 6,500 〇 [Synthesis Example A-2] In addition to the 4-octyloxybenzoic acid, 3.6 g of the formula exemplified as one of the compounds represented by the above formula (5) is used ( 5-7) In addition to 4-(4-pentylcyclohexyl)benzoic acid (pretilt component 2), it was operated in the same manner as in Synthesis Example A-1 to obtain 13.4 g of polyorganosiloxane compound A-2. powder. The Mw of A_2 is 7,900. [Synthesis Example A-3] 9.8 g of polyorganooxynonane S having an epoxy group and 28 g of decyl isobutyl ketone obtained in the above Synthesis Example s-1 were added to a 100 mL three-necked flask, and the above synthesis example 8.0 g of the specific carboxylic acid obtained in 2, 4-(4-pentylcyclohexyl)benzoic acid represented by the above formula (5-7) (pretilt component 2) 14 g and uCAT 18X (quaternary amine salt manufactured by san_apro) 2〇g, at 8〇〇c, the mixing time is given. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. After washing the solution three times, the solvent was distilled off to obtain a white powder of i 3 9 g of polyorganomethoxy hydride compound A-3. The Mw of a-3 is 8,900. [Synthesis Example A-4] Into a 100 mL two-necked flask, 9 to 8 g of the polyorganooxynonane S-1 having an epoxy group selected from the above Synthesis Example S-1, 28 g of mercaptoisobutyl ketone, and -90- were added. 201229139 2.0 g of the specific carboxylic acid i obtained in the above Synthesis Example 2, 4-(4-pentylcyclohexyl)benzoic acid represented by the above formula (pretilt component 2) 5 8 g and 18X (four manufactured by san-apr〇) Grade amine salt) 〇 2〇g, at 8〇. Mix underarm for η hours. After the completion of the reaction, reprecipitation was carried out with decyl alcohol, and the precipitate was dissolved in ethyl acetate to obtain a solution. After washing the solution three times, the solvent was distilled off to obtain a white powder of 13.4 g of polyorganomethoxy oxy hydride compound A-4. A, the number is 7,600. [Synthesis Example A-5] In the same manner as in Synthesis Example a-1 except that the specific carboxylic acid 1 was used instead of 6 8 g of the hydrazine carboxylic acid 3 obtained in Synthesis Example 8, 丨 4 7 g of polyorganismite was obtained. A white powder of Compound A-5 was burned. The Mw of a-5 is 8,1〇〇. The sesquiterpene oxide having an acrylonitrile group is as follows, (sesquioxane having an acrylonitrile group) AC-SQ: "AC-SQ TA-100", manufactured by Toagosei Co., Ltd. [Synthesis Example A-6] [Reaction of sesquiterpene oxide having propylene sulfhydryl group and nucleophilic compound (thiol)] Adding half of a propylene group to a 500 mL three-necked flask equipped with a stirrer and a thermometer矽 alkane AC-SQ ΤΑ-1〇〇 (manufactured by Toagosei Co., Ltd.) 16, 〇g, n-dodecyl-indole thiol (DT) 4 〇.5g as a nucleophilic compound (AC-SQ propylene oxime) The reaction was carried out by heating acetonitrile i6 〇 mL as a solvent and 22.3 g of triethylamine as a catalyst, heating to 50 ° C, and stirring for 90 minutes. After completion of the reaction, the organic layer was extracted, washed with a 0.2% by mass aqueous solution of nitric acid until the water after washing was neutral, and the solvent and the catalyst were distilled off under reduced pressure to obtain a viscous 205.0 g of polyorganosiloxane A-6.透-91 - 201229139 The liquid-to-liquid phase of the S-polyorganosiloxane is determined by GPC. The average weight of the polystyrene-converted J-knife 罝 M w is 5,90 〇. [Synthesis Example -7] [Reaction of a hydrolysis condensate having an epoxy group and a carboxylic acid] 80 g of a hydrolysis condensate S2 having a % oxy group obtained in Synthesis Example S 2 was placed in a 2 〇〇 mL three-necked flask, 25.0 g of mercaptoisobutyl ketone as a solvent, 33.8 g of cardiooctyl benzoic acid (pretilt component 1) as a slow acid, and ucat 18X as a catalyst (hardening accelerator of epoxy compound manufactured by san-apro) 0g, stirring was carried out for 48 hours under i〇〇〇c. After the completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water three times. After drying over magnesium sulfate, the solvent was distilled off to obtain 100.28. The polyoxyalkylene octa-7 was 7. The polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC) was 7,1 Å. [Synthesis Example A- 8] 9.8 g of polyorgano-oxygen S-1 having an epoxy group, methyl iso-y 28 g obtained in the above Synthesis Example sd, and 8.0 g of a specific slow acid obtained in the above Synthesis Example 2 were placed in a 100 mL three-necked flask. 1. Spearic acid 5 ξ-cholesteril-3-yl (pretilt component 3) 2.6 g and UCAT 18X represented by the above formula (5-6) The quaternary amine salt manufactured by san-apro) 〇.2〇g was stirred at 8 ° C for 12 hours. After the reaction was completed, reprecipitation was carried out with decyl alcohol, and the precipitate was dissolved in ethyl acetate. After washing three times with water, the solvent was obtained to obtain a white powder of 1 5% g of polyorganomethoxy hydride compound A-8. The Mw of A-10 was 9,200 [Synthetic Example A-9] -92 - 201229139 In a 200 mL three-necked flask 80 g of the hydrolysis condensate S-2 having an epoxy group obtained in Synthesis Example S-2, methyl isobutyl _ 25.0 g as a solvent, 42.7 g of a specific carboxylic acid 1 and UCAT 18X as a catalyst (san-apro) were added thereto. 0.8 g of the curing accelerator of the produced epoxy compound was stirred at 1 ° C for 48 hours. After the reaction was completed, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water three times and dried over magnesium sulfate. After that, the solvent was distilled off to obtain 98.2 g of polyorganooxane A-9. The polyorganosiloxane A-9 had a polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC). 8,100. [Synthesis Example A-10] In a 200 mL three-necked flask, 80 g of an epoxy group-containing hydrolytic condensation obtained in Synthesis Example S-2 was added. S-2, 25.0 g of methyl isobutyl ketone as a solvent, 42.7 g of a specific carboxylic acid 1, 28.2 g of 4-octyloxybenzoic acid (pretilt component 1), and UCAT 18X (san-apro as a catalyst) 1.7 g of the curing accelerator of the produced epoxy compound was stirred at 100 ° C for 48 hours. After the reaction was completed, the organic layer obtained by adding ethyl acetate in the reaction mixture was washed 3 times, and dried with sulfuric acid money. Thereafter, the solvent was removed to obtain 125.7 g of polyorganooxane A-10. The polyorganosiloxane A-l? had a polystyrene-equivalent weight average molecular weight Mw of 10,200 as measured by gel permeation chromatography (GPC). [Synthesis Example A-1 1; | In place of 4-octyloxybenzoic acid (pretilt component 1) 28.2 g, 4-(4-pentylcyclohexyl)benzoic acid represented by the above formula (5-7) was used ( In addition to the pretilt component 2) of 30.9 g, i28.5 g of polyorganoxanthene A-1 1 was obtained as in Synthesis Example A-10. The polyphenylene oxide-reduced poly(ethylene oxide)-measured weight average molecular weight Mw measured by gel permeation chromatography -93-201229139 (GPC) was 11,500. [Synthesis Example A-12] In a 200 ml three-necked flask, 60 g of a hydrolysis condensate S-3 having an epoxy group obtained in Synthesis Example s 3, and a mercapto-isobutyl group as a solvent were added. 20.0 g, 20.1 g of a specific carboxylic acid 2, and UCAT 18X (a hardening accelerator for an epoxy compound manufactured by San-apro) as a catalyst, 5 g, were mixed at 100 ° C for 48 hours to carry out a reaction. After the completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water three times, dried over magnesium sulfate, and then evaporated to give 5 6 -8 g of polyorganooxane a-12. The polyorganosiloxane A-1 2 had a polystyrene-equivalent weight average molecular weight Mw of 8,600 as measured by gel permeation chromatography (GPC). [Synthesis Example A-13] 6 〇g of the hydrolysis condensate S-3 having a % oxy group obtained in Synthesis Example s_3, and thiol isobutyl ketone as a solvent were added to a 200 mL three-necked flask. .lg specific carboxylic acid 4, 4-(4-pentylcyclohexyl)benzoic acid represented by the above formula (5-7) (pretilt component 2) 12 3 § and UCAT 18X as a catalyst (epoxy compound manufactured by san-apro) Hardening accelerator) 〇.6g 'The reaction was carried out by stirring at 10 ° C for 48 hours. After completion of the reaction, the organic layer obtained by adding ethyl acetate in the reaction mixture was washed with water three times, dried over magnesium sulfate, and then evaporated, and then, 55.9 g of polyorganoxane A-13 was obtained. The weight average of the polyethylene measured by gel permeation chromatography (GPC) for the δH polyorganic shirt 7 ^ Λ 1 Λ - alkane A] 3' was 8,300 in terms of the average molecular weight Mw of 8 7 &amp; [Synthesis Example A -1 4] Into a 100 mL three-necked flask, 10-g - 201229139 obtained in the above Synthesis Example S-4, 10 g of a polyorganosiloxane having an epoxy group, and 20 g of decylisobutylamine were added. 4.35 g of the specific carboxylic acid 5 and UCAT 18X (the quaternary ammonium salt of San-apro) obtained in the above Synthesis Example 13 were 0.10 g at 8 Torr. (: stirring for 12 hours. After the reaction was completed, reprecipitation was carried out with methanol, and the precipitate was dissolved in acetic acid to obtain a solution. After washing the sigma solution three times, the solvent was taken out to obtain 10.9 g of polyorganismite. The white powder of the compound A-14 was oxy-fired. The Mw of the polyorgano-oxygenated compound A-14 was 6,400. [Synthesis Example A-15] The l obtained in the above Synthesis Example S-4 was added to a 100 mL three-necked flask.聚g polyorganooxy siloxane S-4 having an epoxy group, fluorenyl isobutyl ketone 2 〇 g, 6.95 g of a specific carboxylic acid 5 obtained in the above Synthesis Example 13, and 4-(4) represented by the above formula (5-7) -pentylcyclohexyl)benzoic acid (pretilt component 2) 154 § and UCAT 18X (quaternary amine salt manufactured by san-apro) 〇.2〇g, sandalwood at 8 ° C for 12 hours. After re-precipitation with decyl alcohol, the solution was dissolved in ethyl acetate to obtain a solution. After washing the solution three times, the solvent was obtained to obtain 1 3.7 g of polyorganosiloxane compound A-1 5 white. The Mw of the polyorganosiloxane compound A-1 5 is 7,700. [Synthetic Example A-1 6] In addition to the 4-(4-pentylcyclohexyl)anene represented by the above formula (5-7), 1.54 g of a citric acid, and 15.5% of a ruthenium succinic acid-containing succinic acid (pretilt component 3) represented by the above formula (5-6), and 15. lg of a synthetic organic oxime A white powder of the compound A-16 was burned. Polyorganic; the Mw of the oxalyl compound A-16 was 8,200. [Synthesis Example A -1 7] The -95- obtained in the above Synthesis Example S_4 was added to a 100 mL three-necked flask. 201229139 l〇g polyorganooxynonane S_4 having an epoxy group, 2〇g of methyl isobutyl ketone, 7.2 6 g of a specific carboxylic acid obtained in the above Synthesis Example 3, 3,4-octyloxybenzoic acid (pretilt angle) Ingredient 1) 3.52g and UCAT 18X (quaternary amine salt manufactured by san-apro) 〇.20g 'at 80. (: stirring for 12 hours. After the reaction is over, reprecipitation with methanol is carried out) The precipitate is dissolved in acetic acid In the ester, a solution was obtained, and the solution was washed with water three times, and then the solvent was distilled off to obtain a white powder of 158 g of a polyorganosiloxane compound A-1 7. The Mw of the polyorganosiloxane compound A_丨7 was 9,100. [Synthetic Example A-18] 4-(4-pentylcyclohexyl) represented by the above formula (5-7), except for the substitution of 4-octyloxybenzoic acid (pretilt component 丨) 3 5 2 g Benzoic acid (pretilt component 2) 3.8 6 g, as in Synthesis Example a -1 7 , a white powder of 1 5.4 g of polyorgano-oxygenated compound A -1 8 was obtained. Polyorganismite compound A The Mw of -1 8 is 8,900. [Synthesis Example A-19] In addition to 7.27 g of the specific carboxylic acid 3, 15 5 g of a polyorganosiloxane compound A was obtained in the same manner as in Synthesis Example A-17 except that 6.17 g of the specific carboxylic acid 6 obtained in the above Synthesis Example 15 was used. -1 of 9 white powder. The Mw of the polyorganosite compound A-19 was 9,100 » [Synthesis Example A-20] In addition to the substitution of 7_26 g of the specific carboxylic acid 3, 5.78 g of the specific carboxylic acid 7 obtained in the above Synthesis Example 16 was used, and the synthesis was carried out. Example A-17 - Oak, a white powder of 15.3 g of polyorganophosphorus compound A-20. The polyorganooxalate compound A-20 had a Mw of 9,000. [Synthesis Example A-21] -96-201229139 In the same manner as in Synthesis Example A-1 7 except that 7.26 g of the specific carboxylic acid 3 was used instead of the 7.1 8 g of the specific carboxylic acid 8 obtained in the above Synthesis Example 17, 15.6 g was obtained. A white powder of polyorganotite compound A-21. The Mw of the polyorgano-oxygenated compound A-21 was 9,300. [Synthesis Example A-2 2] In addition to 7.26 g of the specific carboxylic acid 3, 15.2 g of a polymer was obtained in the same manner as in Synthesis Example A-1 7 except that 6 · 18 g of the specific carboxylic acid 9 obtained in the above Synthesis Example 18 was used. A white powder of the organic oxalate compound A-22. The Mw of the polyorganosiloxane compound A-22 was 8,900. [Synthesis Example A-23] In addition to 7.27 g of the specific carboxylic acid 3, except that 7.07 g of the specific carboxylic acid 10 obtained in the above Synthesis Example 19 was used, as in Synthesis Example A-17, 15.8 g of a polyorganosiloxane compound was obtained. A-23 white powder. The Mw of the polyorganosulfonated compound A-23 was 9,500. [Synthesis Example A-24] In the same manner as in Synthesis Example A-1 7 except that 8.26 g of the specific carboxylic acid 3 was used instead of 8.289 g of the specific carboxylic acid 1 obtained in the above Synthesis Example 20, 15.6 g of polyorganofluorene was obtained. A white powder of the alkane compound A-24. The polyorganosiloxane compound A-24 had a Mw of 9,200. [Synthesis Example A-25] In the same manner as in the synthesis example A -1 7 except that 7.26 g of the specific carboxylic acid 3 was used instead of the specific carboxylic acid 1 2 obtained in the above Synthesis Example 22, 15.5 g of a polymer was obtained. A white powder of an organic oxoxane compound A-25. The Mw of the polyorganooxygenated compound A-19 was 9,100. The synthesis results of the above polyorganosiloxane compound (A) are summarized in the following Table -1, and the "-" in Table 1 indicates that the compound is not used. [Table 1] Polyorganosiloxane (8) Polyorganosiloxane precursor, specific carboxylic acid, other pretilt-developing compound, weight average molecular weight, yield (g), amount of use (mol%), amount of use (mol%), synthesis Example Α-1 Α-1 S-1 Specific carboxylic acid 1 25 Pretilt component 1 25 6,500 14.5 Synthesis Example Α-2 Α-2 S-1 Specific carboxylic acid 1 25 Pretilt component 2 25 7,900 13.4 Synthesis Example Α-3 Α-3 S-1 Specific carboxylic acid 1 40 Pretilt component 2 10 8,900 13.9 Synthesis example Α-4 Α-4 S-1 Specific carboxylic acid 1 10 Pretilt component 2 40 7,600 13.4 Synthesis example Α-5 Α-5 S -1 Specific carboxylic acid 3 25 Pretilt component 1 25 8,100 14.7 Synthesis Example Α-6 Α-6 AC-SQ - - DT 20 5,900 205.0 Synthesis Example Α-7 Α-7 S-2 - - Pretilt component 1 30 7 , 1〇〇100.2 Synthesis Example Α-8 Α-8 S-1 Specific carboxylic acid 1 40 Pretilt component 3 10 9,200 15.5 Synthesis Example Α-9 Α-9 S-2 Specific carboxylic acid 1 25 - - 8,100 98.2 Synthesis Example Α-10 Α-10 S-2 Specific carboxylic acid 1 25 Pretilt component 1 25 10,200 125.7 Synthesis Example Α-11 Α-11 S-2 Specific carboxylic acid 1 25 Pretilt component 2 25 11,500 128.5 Synthesis Example Α-12 Α -12 S-3 specific carboxylic acid 2 25 - - 8, 600 56.8 Synthesis Example Α-13 Α-13 S-3 Specific carboxylic acid 4 10 Pretilt component 2 20 8,3〇〇55.9 Synthesis Example Α-14 Α-14 S-4 Specific carboxylic acid 5 25 - - 6,400 10.9 Synthesis Example Α-15 Α-15 S-4 Specific carboxylic acid 5 40 Pretilt composition 2 10 7,700 13.7 Synthesis Example Α-16 Α-16 S-4 Specific carboxylic acid 5 40 Pretilt component 3 10 8,200 15.1 Synthesis Example Α-17 Α-17 S-4 Specific carboxylic acid 3 25 Pretilt component 1 25 9,100 15.8 Synthesis example Α-18 Α-18 S-4 Specific carboxylic acid 3 25 Pretilt component 2 25 8,900 15.4 Synthesis example Α-19 Α-19 S -4 Specific carboxylic acid 6 25 Pretilt component 1 25 9,1〇〇15.5 Synthesis Example Α-20 Α-20 S-4 Specific carboxylic acid 7 25 Pretilt component 1 25 9,000 15.3 Synthesis Example Α-21 Α-21 S -4 Specific carboxylic acid 8 25 Pretilt composition 1 25 9,300 15.6 Synthesis Example Α-22 Α-22 S-4 Specific carboxylic acid 9 25 Pretilt component 1 25 8,900 15.2 Synthesis Example Α-23 Α-23 S-4 Specific carboxy Acid 10 25 Pretilt composition 1 25 9,500 15.8 Synthesis Example Α-24 Α-24 S-4 Specific carboxylic acid 11 25 Pretilt composition 1 25 9,200 15.6 Synthesis Example Α-25 Α-25 S-4 Specific carboxylic acid 12 25 Pre Inclination component 1 25 9,100 15.5 Other pretilt angles in Table 1 above The present compounds are shown in the following compounds. Further, the amount used (% by mole) is represented by mol% relative to Si atoms in the polyorganosiloxane precursor. Pretilt component 1 : 4-octyloxybenzoic acid pretilt component 2 : 4-(4-pentylcyclohexyl)benzoic acid pretilt component 3 : succinic acid 5 ξ - cholestane-3-yl <polymer (Β Synthesis] -98- 201229139 [Synthetic Example Pl] Dissolving cyclobutane tetraphthalic acid dianhydride 19_61 g (〇_i mole) and 44,_2 in 367.6 g of N-methyl-2-pyrrolidinone Amino 2,2'-dimethylbiphenyl 2 1 · 2 3 g (0.1 mol) 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 temple was washed with methanol and dried under reduced pressure. Drying under the pan for 15 hours gave 35 g of poly-proline acid PA-1. [Synthesis Example P-2] 1 8 85 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid, and 8 84 g as a diamine were dissolved in 140 g of N-methyl-2-pyrrolidone The diamine represented by the following formula (G-4) of the compound and 7.31 g of para-aniline were reacted at 60 ° C for 4 hours. The viscosity of the polymerization solution was measured and found to be 2,15 〇nlPa.s. The reaction solution was poured into an excess of sterol to precipitate a reaction product. Then, it was washed with methanol under reduced pressure. Drying under the arm for 24 hours gave polyamic acid. The obtained polylysine was all redissolved in 465 g of N-mercapto-2-dehydrazine. Add pyridine 6 _ 6 5 g and acetic anhydride 8.5 9 g at 1 Hz. (: dehydration ring closure was carried out for 4 hours). As described above, precipitation, washing, and depressurization were carried out to obtain 2 3.1 g of polyimine imine p I _ 1 having an azetization ratio of 50%.

-99- 201229139 Dissolved 24.94g of 2,3,5-trimethylcyclopentyl acetic acid dianhydride as tetrazoic acid diterpene in 200gN-mercapto-2-oxaridinone, as a gas _ _ F horse The amine compound represented by the following formula (G-5), the diamine 1 l.24 g and the 3,5-diamine spirit, were 13.82 g from the crude soil, and reacted at 60 ° C for 4 hours. The viscosity of the polymerization solution was measured to be 1,40 mPa.s. The reaction solution was poured into a large amount of the reaction product of a large amount of "A", and then washed with methanol and dried under reduced pressure at 4 Torr for several hours to obtain polylysine. Dissolved, 450g of N-mercapto-2-pyrrolidone, adding pyridine 13 2〇g and acetic anhydride 17.04g 'dehydration ring closure at ll ° ° C for 4 hours, and sinking as described above

The mixture was washed, washed, and dried under reduced pressure to give &lt;RTI ID=0.0&gt;&gt; A

2,3,5-trisylcyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, 23 〇6 g, 3,5-diamine as a diamine compound, dissolved in 200 g of N-f-based 2-pyrrolidinone The benzoic acid hydrazone 1 〇1, 10.81 g of the diamine represented by the above formula (G_4) and the 512 g of the diamine represented by the above formula (G_5) are (9). Underarm reaction 4] When the viscosity of the 4 4 liquid mixture is 丨, 3 QQmpa · s. The reaction solution was poured into an excess of methanol to precipitate a reaction product. Then, with methanol/month; first, it was dried at 4 ° C for 24 hours under reduced pressure to obtain polylactoic acid. [Synthesis Example P-4] -100 - 201229139 The obtained polyamic acid was all redissolved in 45 〇g of N-mercapto-2-pyrrole. In the ketone, 8.1 4 g of pyridazole and 1.00 g of acetic anhydride were added to carry out dehydration ring closure at 11 ° C for 4 hours, and precipitation, washing and drying under reduced pressure were carried out to obtain 30.5 g of ruthenium imidization ratio. 55% polyimine PI-3. &lt;Preparation of Liquid Crystal Aligning Agent&gt; [Example 1] The solution containing poly-proline PA_丨 obtained in the above Synthesis Example P-1 was converted into a polyglycine p A -1 contained therein to be 1 〇 An equivalent amount of 〇 parts by mass, wherein 5 parts by mass of the above polyorganosiloxane compound A- 5 parts by mass of the above polyorganosiloxane compound a_6 is added as another polymer, and further N-methyl 2 -pyrrole is added thereto. The ketone and butyl cellosolve were prepared into a solution having a solvent composition of N-mercapto-2-pyrrolidone: butyl cellosolve = 5 〇: 5 Torr (mass ratio) and a solid concentration of 3.5% by mass. This solution was filtered through a filter of pore size 〇 .2 μηι to prepare a liquid crystal alignment agent E-1. &lt;Production and Evaluation of Liquid Crystal Cell&gt; Using the liquid crystal alignment agent prepared above, the pattern (two types) of the transparent electrode and the ultraviolet irradiation amount (three levels) were changed as described below, and a total of six liquid crystal display elements were produced and evaluated. [Manufacturing of Liquid Crystal Cell Having Unpatterned Transparent Electrode] A transparent electrode surface of a glass substrate having a transparent electrode of a light-shielding 4X structure having an I τ film is coated with a spin coating method. The liquid crystal alignment agent £-1 of the above-mentioned I was subjected to a 1 minute error on a hot plate of 8 ° C for a pre-heating of the knife clock, and then, in a nitrogen-substituted baking phase, at a temperature of 200 ° C, n士Λ,,, ...1小日守'The formation of a coating film with a thickness of 0.08μιη (liquid day alignment film). This operation was repeated to prepare F I as a pair of (two) substrates having a liquid crystal alignment film. -101 201229139 With respect to the β-coat film, rubbing was carried out by using a friction device having a view of winding a rayon cloth at a speed of 4 GGnm, a stage moving speed of 3 cm/sec, and a thief press-in length of 0.1. _, enter in ultrapure water minutes = ultrasonic cleaning, then at 100. The substrate was dried in a dust-free oven for 1 minute, and a substrate having a liquid crystal alignment film was obtained. This operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Next, an epoxy resin adhesive having an alumina sphere of 5.5 μm in diameter was applied to the outer edge of the liquid crystal alignment film of one of the pair of substrates, and then the liquid crystal alignment film surface was pressed against the surface to harden the binder. Then, a nematic liquid crystal (manufactured by Merck, MLC-6608) was filled between the pair of substrates by the liquid crystal injection port, and then the liquid crystal cell was injected with an acrylic photocurable adhesive to produce a liquid crystal cell. The above operation was repeated to manufacture three liquid crystal cells having unpatterned transparent electrodes. One of them directly evaluates the pretilt angle described later. The remaining two liquid crystal cells were irradiated with light in a state where a voltage was applied between the IT electrodes by the following method, and then supplied to the evaluation of the pretilt angle and the voltage holding ratio. Two of the above-mentioned liquid crystals 70 were respectively applied with an alternating voltage of 10 Hz at a frequency of 60 Hz between the electrodes of the I Τ , to drive the liquid crystal, and the ultraviolet ray irradiation device using the light source was a metal hydride lamp, and the ultraviolet ray was 10,000 J/m 2 . Or an irradiation dose of 100,000 J/m2. Further, the irradiation amount is a value measured using an exposure meter measured with a wavelength of 3 6 5 n m as a reference. [Evaluation of Pretilt Angle] Each of the liquid crystal cells manufactured as described above is based on Non-Patent Document No. 102-201229139 2 (TJ Scheffer et. al., J. Appl. Phys. vo. 48, p. 1783 (1977)) and The method described in Non-Patent Document 3 (F. Nakano et. al., JPN. J. Appl. Phys. v. 19, p. 20 1 3 (1 980)) by using a He-Ne laser The angle at which the liquid crystal molecules measured by the crystal rotation method are inclined from the substrate surface serves as a pretilt angle. The liquid crystal cell not irradiated with light, the liquid crystal cell having an irradiation amount of 10,000 J/m 2 , and the irradiation amount 100, and the pretilt angles of the liquid crystal cells of 〇00 J/m 2 are shown in Table 2 [Evaluation of voltage holding ratio] The liquid crystal cell was applied with a voltage of 5 V for 60 μs at a pitch of 167 msec at 23 ° C, and then the voltage holding ratio after 167 msec from the release of the pressurization was determined. The measurement device used in the liquid crystal cell of the VHR-1 照射 irradiation amount of 10,000 J/m2 and the liquid crystal cell of the irradiation amount of 10,000 J/m2 manufactured by TOYO TECHNICA Co., Ltd. are shown in Table 2. [Manufacturing (1) of Liquid Crystal Cell Having Patterned Transparent Electrode] The surface of each of the glass substrates a and B of the ITO electrode divided into a plurality of regions having the slit-like pattern shown in Fig. 1 The liquid crystal alignment agent E-1 prepared above was applied by a spin coating method, and heated on a hot plate at 80 ° C for 1 minute (preheating) to remove the solvent, and then placed in a nitrogen-substituted oven at 2 Torr. The film was heated for 1 hour to form a coating film (liquid crystal alignment film) having a film thickness of 〇8 μm. This operation is repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Next, an epoxy resin adhesive having a diameter of 5 · 5 μηη alumina balls was applied to the outer edge of the liquid crystal alignment film of one of the pair of substrates, and the liquid crystal alignment film surface was pressed against the 'hardenable binder'. Then, from -103 to 201229139, a liquid crystal cell was filled with a nematic liquid crystal (manufactured by Mercke, MLC-660 8) between the pair of substrates, and the liquid crystal cell was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. The above operation was repeated to fabricate three liquid crystal cells having patterned transparent electrodes. One of them is directly supplied to the reaction rate valence described later. The remaining two liquid crystal cells are irradiated with light at a dose of 10,000 J/m 2 or 100,000 J/m 2 in a state where a voltage is applied between the conductive films in the same manner as in the production of the liquid crystal cell having the unpatterned transparent electrode. To the evaluation of the reaction rate. Further, the electrode pattern used here is the same kind of pattern as the electrode pattern of the PS A mode. [Evaluation of Reaction Rate] The respective liquid crystal cells manufactured as described above were not subjected to a voltage, and the visible light was irradiated, and the value of the light transmittance transmitted through the liquid crystal cell was measured by a photo multimeter as the relative transmittance 〇 %. Next, an alternating current voltage of 6 〇 V was applied between the electrodes of the liquid crystal cell, and the transmittance at this time was measured in the same manner as described above, and this value was taken as the relative transmittance of 1 〇 〇 〇 / 〇. At this time, when an alternating voltage of 6 〇 V was applied to each liquid crystal cell, the relative transmittance was measured from 10 ° /. Conversion to 90% of the time' This time was defined as the reaction rate and was evaluated. The liquid crystal cell which was not irradiated with light, the irradiation amount of 1 〇, the liquid crystal cell of 〇〇〇J/m2 and the liquid crystal cell of ϊ100,0〇〇J/m2 were shown in Table 2, respectively. [Manufacturing of Liquid Crystal Cell Having Patterned Transparent Electrode (2)] Using the liquid crystal alignment agent prepared above, glass substrates A and B each having an I Τ 0 electrode having a fishbone pattern shown in Figs. 2 - 104 to 201229139 were used. In the same manner as in the manufacture of the liquid crystal cell having the patterned transparent electrode (1), a liquid crystal cell having no light irradiation and a liquid crystal cell having an irradiation amount of 10,000 J/m 2 and a liquid crystal cell of 100 J/m 2 are respectively formed. The evaluation of the reaction rate was supplied as described above. The evaluation results are shown in Table 2. [Examples 2 to 34 and Comparative Examples 1 and 2] In the above Example 1, the kind and amount of the polymer (B) and the polyorganosiloxane (A) (component 1 and component 2 added as needed) A liquid alignment agent was prepared in the same manner as in Example 1 except that the liquid crystal alignment agent was produced using the liquid crystal alignment agent, and the evaluation results are shown in Table 2. The upper system and the object crystal -105 201229139 [Table 2] The amount of JH) the liquid reaction speed of the electrode (msec.) UV irradiation (J/m2) 100,000 two CNJ σ> two inches two CM m inch CM two CO two CO 2 CM o 2 inch CO O Oi O CT) inch 2 CO σ&gt; 00 GO σ&gt; 00 σ&gt; CO 10,000 _I CSJ CSJ CO O) CO CM GO CO eg inch CD 卜 03 in CO CNJ σ&gt; CO cvj s 00 00 in CM CM CO inch LO to LT&gt; m inch inch 〇CO C0 ss CO CO another 00 CO CO eg 00 CSJ CO CO CM CD CO CNJ in CO CSI CO another 05 CM CO CM \r&gt; CO &lt;N CO Κ ( D CM csj (liquid reaction rate of Ο CM amount floating electrode (msec.) ultraviolet irradiation amount (J/m2) σ σ gt> LO CO CO CM to CM in CNi &lt;£&gt; o CO CM CM 00 α&gt; 00 in CNI ίο CM CM 00 CO 卜二CM CM 卜二 oo 〇Ο 二〇Ο 05 co 00 CM 10,000 CO CNi ΙΩ &lt;Μ s CSi CM σ&gt; CM Art CO CO CNi eg 00 σ&gt; CVi &lt ;〇CMJ 卜又oo CM CO csj σ&gt; s CO CM to to CD to if&gt; CD 〇ΓΟ CO CO σ&gt; eg &lt;〇CO S oo CO E5 CD CM 00 CM CO CO 05 CM CO CO σ&gt; CM in CO CNJ CO 05 CM in CO CM CO 5 00 0*4 to CSI 5 &lt;〇CM 00 Cvi ss Liquid crystal cell voltage retention ratio (%) with unpatterned electrode UV irradiation S (J/m2) 100,000 σ&gt; L 99.2 1 丨99.3 1 I 99.3 I 1 99.2 1 (J) σ&gt; CO ai σ&gt; L 99.4 II 99.1 | | 9_M— I 99.2 I 1 99.4 I 1 99.3 1 1 99.4 i 1 99.2 1 I 99.2 II 99.1 ! 1 99.2 i 1 99.2 1 1 99.4 1 1 99.4 1 1 99.2 1 1 99.2 1 1 99.4 1 1 99.3 I 1 99.4 1 1 99.4 1 I 99.4 1 1 99.4 1 々σ&gt;σ&gt; 99.4 I inch ai σ &gt; 99.4 | CO σ &gt; σ &gt; , 99.0 I 10,000 CO σ &gt; σ &gt; 1 99.3 1 1 99.5 1 I 99.5 I vs σ &gt; I 99.3 II 99.4 II 99.3 II 99.6 II 99.3 II 99.6 | I 99.4 I 1 99.6 1 1 99.5 1 1 99.6 1 1 99.3 1 I 99.4 I 1 99.3 j 1 99.4 1 1 99.4 1 1 99.6 1 1 99.5 1 1 99.4 1 1 99.3 1 1 99.6 1 1 99.4 I 1 99.6 1 1 99.6 1 I 99.6 1 &lt;〇σ&gt;σ&gt; 1 99.6 1 I 99.6 II 99.6 | I 99.6 I co ai σ> :99.1 I Pretilt angle Γ UV irradiation fi(J/m2) 〇〇〇οο 1 83.6 1 1 81.0 j I 83.5 I 1 87.3 I 81.3 1 I 8 7.4 | CO oo I 88.2 II 83.7 I 87.3 I 81.5 1 86.7 1 1 87.2 00 in 00 o δ 1 86.5 1 1 86.3 1 1 86.5 1 丨86.9 1 1 86.8 1 1 87.5 | 87.8 | 87.3 1 1 87.5 | 87.4 1 δ 87.4 I CM ES '87.4 I 81.3 I 〇〇〇' CM 00 ο I 86.0 II 86.6 I 1 88.9 1 1 86.2 1 I 88.7 | σ&gt; 00 I 89.2 II 87.0 | I 88.3 II 86.1 I o 00 00 1 88.5 I 1 88.4 1 1 87.3 | I 88.2 I 1 88.6 1 c〇S L87JI 1 87.5 | 1 88.8 I 1 88.0 1 1 88.5 1 1 88,2 1 〇6 00 [88.9 1 88.3 1 ,88.2 1 1 88.3 1 88.3 1 88.2 II 88.3 II 88.2 I CSJ QO OO 86.2 I 〇00 σ&gt; οο 1 89.9 1 I 89.9 I σ&gt; σ) 00 1 89.9 1 1 89.8 1 I 89.8 I I89.8 II 89.9 II 89.9 II 89.9 II 89.8 I 1 89.9 1 1 89.9 1 1 89.9 1 1 89.8 II 89.9 I 1 89.8 1 1 89.8 1 I 89.9 1 丨89,9 1 1 89.9 1 1 89.8 1 1 89.8 1 1 89.9 1 1 89.8 1 1 89.9 1 i 89.9 1 1 89.9 1 1 89.9 1 ! 89.9 1 89.9 II 89.9 I 89.9 | C7) ai 00 89.8 I Polyorgano hydrazine compound (A) (combination amount with respect to 100 parts by mass of polymer (B)) Component 2 Preparation amount (parts by mass) ο LO In o CO CO CO in in CO CO 1 CO 1 CO I CO 1 1 1 CO CO in CO CO 1 CO c〇c〇CO CO CO CO in o Species CD I &lt; 1 Α-7 1 CO 1 &lt; 〇CO I 〇&lt; 1 &lt; 1 AC-SQI CD I &lt; CO &lt; I A-7 CO I &lt; 〇¢0 I o &lt; CD 1 &lt; 1 [a-7 丨1 CO 1 &lt; I 1 AC-SQI 1 1 1 CD 1 &lt; 〇( O 1 〇&lt; 1 AC-SQI CD 1 &lt; 1 AC-SQI 1 ο to 1 ο &lt; 〇(D 1 〇σ CO 1 o σ CO 1 ο &lt;〇u&gt; I 〇&lt; I AC-SQI I AC-SQI I &lt; 1 I &lt; Ingredient 1 Blending 5 (parts by mass) ΙΤ5 ooo in in ao in o in o in LO in in oo to tn o io o ο oo ο oo 〇 II Category 1 &lt; CM 1 &lt; 00 1 &lt; I A-3 | 1 A-4 | 00 1 &lt; I A-2 II a-4 | I A-4 | I A-5 jl A-2 I CO 1 &lt;σ&gt;&lt;; O) 1 &lt; 〇T &lt; o T &lt; Τ Ι &lt; r- &lt; 1 A-12| LA-121 LA-131 | A-141 LO 7 &lt; CD T &lt; ω T &lt; T &lt; 00 T &lt; Ο) τ &lt;&lt;&lt; CSJ CM 1 &lt; co &lt;NI &lt;&lt; in eg I &lt; II Polymer (B) τ~ 1 &lt; Q. Τ Ι &lt;; 1 PA-1 II PI-1 1 I PI-1 I 1 Pi-1 II PI-2 I I- PI-2 II PI-2 II PI-2 l I PI-2 I 1 PI-2 丨1 EI PI-2 1 丨PI-1 I 1 PI-1 I l PI-2 I LPh-21 1 PI-3 1 LBr-31 1 PI-2 1 CO 1 0: 1 PI-1 1 1 0: :PI-2 I LPI-31 T— E 1 δ: 0: ! PI-1 IT·- CL r~ 0: τ- Ι 0: r— ID: 丄;1酽11 CN 1 LU CO I UJ 1 E-4..II E -5 i (DI LU I E-7 | 00 I UJ 0&gt; I UJ 〇T UJ r~ T LU IE-121 CO T LU inch T UJ IE-151 CD T UJ T Lit 00 T LLI T LU 8 LU r *· CM 1 LU CSJ CM I LI) CO CVJ 1 m UJ Lf) CsJ LU CO CNJ m csi m ω CM mountain σ&gt; eg 1 UJ LU I UJ CN CO I LU CO co I LU inch CO I LiJ T&quot;- I LU 〇ICE-2! ϊ m κ CM 匡m κ CO 匡m K inch m K in 匡m K to 匡mw 卜{« CO 匡m K σ&gt; S mwi 闺w 5 m K &lt;N imw CO im K inch im H in 5 m K CD Ϊ m K im [K GO ί m K σ> Ϊ 63⁄4 匡m 肫 leather mw CNI (N mi£i K CO CVi 匡m K 5 monument M LO CM 匡m CD 匡m K c\i 匡埕Μ 00 CN) 荜m (W σ&gt; (N 匡m CO m 闺Ά CM CO m grip K CO CO m 1£) K m K i Age a CM &amp; u -106- .201229139 As can be seen from the results of Table 2, in the method of the present invention, the amount of ultraviolet irradiation is 100,000 &lt;1112 (1 &gt; 8 Currently used values. The degree of the pretilt angle obtained by the irradiation is excessive, and the pretilt angle obtained by the irradiation amount of 10, 〇〇〇j/m2 or less is suitable. Further, even when the amount of irradiation is small, a sufficiently fast reaction rate can be obtained, and the voltage holding ratio is also excellent. Therefore, the method according to the present invention can realize the advantages of the PSA mode with a small amount of light irradiation, and can manufacture a liquid crystal display element having a liquid crystal reaction speed faster than that of the current PSa mode liquid crystal display element. [Industrial Applicability] According to the present invention, it is possible to provide a method of manufacturing a liquid crystal display element which has a wide viewing angle and a fast anti-deer speed of liquid crystal molecules, and which is excellent in display characteristics and long-term reliability. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a transparent conductive film pattern in a liquid crystal cell having a patterned transparent conductive film produced in Examples and Comparative Examples. Fig. 2 is a view showing an example and a comparative example. Description of the transparent conductive film pattern in the liquid crystal cell having the patterned transparent conductive film produced [Main element symbol description] 1 ITO electrode 2 slit portion 3 light shielding film-107-

Claims (1)

201229139 VII. Patent Application Range: 1 . A method of manufacturing a liquid crystal display element, comprising the steps of: (1) forming a coating film on the conductive film of a pair of substrates having a conductive film using a liquid crystal alignment agent; The liquid crystal alignment agent contains [A] a polymer component having a group having a polymerizable carbon-carbon double bond in the same or different polymer and a group represented by the following formula (A 1), (2) a step of arranging a pair of substrates on which the coating film is formed via a liquid crystal layer such that a pair of coating films face each other to form a liquid crystal cell, and (3) applying a voltage between the conductive films of the pair of substrates a step of irradiating the liquid crystal cell with light, R3-{R2-j-R1-(A1) (in the formula (A1), 'R疋-indenylene group, carbon atom-extension group, phenyl group or Extending the cyclohexyl group, some or all of the hydrogen atoms of these groups may be substituted; R2 is a linking group containing any one of a double bond, a triple bond, an ether bond, an vinegar bond, and an atmosphere atom; R3 has at least two single The base of the ring structure, a is 0 or 1). 2. The method for producing a liquid crystal according to claim 1 wherein the [A] compound comprises [A-1] having a binder-incorporating carbon-carbon double bond. A polymer having a group and a group represented by the above formula (A1). 3. For the manufacturing method of the liquid crystal _ 不 不 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 a carbon-carbon double bond-based polymer and [A]^-3] a polymer having a group of the above formula (A1) representing -108 to 201229139. 4. A method of manufacturing a patent, wherein j (R7)_R6- (R5 is a cyclohexyl group or a subdiyl group in the formula (A2), and the (c+1)-valent group in which the base group R5 is a ring-connected ring containing a fluorenyl group, a double bond, or a ring; R7 is an oxycarbonyl group, an alkane; d is 1 or 2; R4, R7 and b are each 5 as in the patent application manufacturing method, and 〇 6. as in the patent application manufacturing method, 7 kinds of acid and polyimine Liquid crystal display (A2) The R3 in the above formula (A1) of the liquid crystal display element according to any one of items 1 to 3 is represented by the following formula (A2): VR4' 'R4 is a phenyl group and a phenyl group. a part or all of a hydrogen atom of a naphthyl group, a cyclohexylene group, a cyclohexyl group or a divalent heterocyclic ring may be substituted; a methylene group having a substituent and a stretching number of 2 to 10 carbon atoms; a triple bond, a snap bond, an ester bond, and at least any of the heterocyclic groups; R6 is a (c+1) hydrogen atom removed from benzene, biphenyl, naphthalene, cyclohexane, dibasic or heterocyclic compounds. The part or all of the hydrogen atom of the root group may be a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkyl group or an alkoxy group; b is 0 or 1, c is an integer of 1 to 9, R, R7 and When each of b is plural, a plurality of R4 and R5 are the same or different. The liquid crystal display element of any one of items 1 to 3 has a polyorgano-oxygenane structure in the first [A] polymer component. The [A] polymer component of the liquid crystal display element of any one of the items 3 to 3 further contains at least one polymer selected from the group consisting of polyamines. The element 'is taken as claimed in claims 1 to 6 A method for producing a liquid crystal display device according to any one of the preceding claims, wherein the liquid crystal display element comprises a liquid crystal alignment agent containing [A] a polymer component, wherein the [A] polymer component is the same or different polymer. a group having a polymerizable carbon-carbon double bond and a group represented by the following formula (A1), R3-fR2 VII R1 - (A1) Formula (A1) R1 is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexylene group, and some or all of the hydrogen atoms of these groups may be substituted; R2 is a double bond, a triple bond, or an ether. a linking group of any of a bond, an ester bond, and an oxygen atom; R3 is a group having at least two monocyclic structures; a is 0 or 1. -110-