TW201235384A - Liquid crystal alignment agent, polymer, method of producing polymer, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which can solve at least one of a problem caused by the usage of a high boiling point solvent and a problem caused by the usage of a solvent having high solubility in a plastic substrate. The liquid crystal alignment agent comprises a polymer having an amic acid ester structure obtained by esterifying a carboxyl group of an amic acid, wherein the amic acid ester structure comprises at least one structure selected from the group consisting of an acetal ester structure of the carboxyl group, an ketal ester structure of the carboxyl group, a l-alkylcycloalkylester structure of the carboxyl group and a t-alkyl ester structure of the carboxyl group.

Description

201235384 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent 'polymer, a method for producing a polymer', a liquid crystal alignment film and a liquid crystal display element, and in detail, 'heating while coating a substrate Further, a liquid crystal alignment agent to be used, a polymer suitable as a constituent component of the liquid crystal alignment agent, a method for producing the polymer, and a liquid crystal alignment film and a liquid crystal display element formed using the liquid crystal alignment agent. [Prior Art] The liquid crystal display element is formed by arranging a liquid crystal display element substrate on which a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided, and simultaneously sealing liquid crystal molecules between the pair of substrates. As the liquid crystal display element, it is known that the long axis of the liquid crystal molecules is continuously twisted from 90 to 90 in the substrate. The so-called TN (Twisted Nematic) type element. In addition, STN (Super Twisted Nematic) type elements with high contrast and low viewing angle dependence (In_Plane Switching) type elements have been developed, compared with tn type elements. An VA (Vertical Aiignment) type element which has a small viewing angle dependency and does not require rubbing treatment when liquid crystal alignment is performed, and an optical compensation f-curve (OCB) type liquid crystal display element which is excellent in viewing angle dependence and excellent in high-speed response of an image screen. As the liquid crystal alignment film used in these liquid crystal display elements, for example, as shown in the patent literature, it is contained in a solvent such as fluorenyl-2-pyrrolidone and γ-butyrolactone to contain polyruthenium. Amine or polyamic acid is obtained to obtain a liquid crystal alignment agent, which is coated on a substrate and then heated by the heating of 4 - 201235384. By using polyimine or polyglycolic acid as a liquid crystal alignment agent, liquid crystal alignment defects excellent in heat resistance, affinity for liquid crystals, mechanical strength, and the like can be obtained. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-241646 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei. 278724A SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] Here, when polyacrylonitrile or polyaminic acid is dissolved to form a liquid crystal alignment agent, it is necessary to use 1 - mercapto-2-pyrrolidine as described above. Ketone and γ_ butyl vinegar and so on. However, if such a solvent is used, a problem arises when a liquid crystal alignment agent is coated on a substrate to form a liquid crystal alignment film. Specifically, '1-methyl-2-pyrrolidone and γ-butyrolactone are solvents having a high boiling point (for example, 200 ° C), and in the case of using such a high boiling point solvent, it is required to form a liquid crystal alignment film. Perform high temperature heating. If this is the case, for example, when a flexible liquid crystal display is developed using a plastic substrate instead of a glass substrate, the plastic substrate may be deformed due to high-temperature heating when the liquid crystal alignment film is formed. Further, the formation of the liquid crystal alignment film is performed for the substrate on which the color filter is formed. For example, when a radiation-sensitive composition containing a dye is used as a color filter, since the heat of the dye is not high, if the liquid crystal alignment film is formed and heated at a high temperature, the color filter may be adversely affected. In addition, when it is necessary to heat the temperature to form a liquid crystal alignment film, for example, the total heat amount of the manufacturing method is increased accordingly, and the amount of carbon dioxide discharged correspondingly increases accordingly. On the other hand, 1-nonyl-2-pyrrolidone and γ-butyrolactone are solvents which have high solubility in a plastic substrate. Therefore, if the use of such a solvent, for example, the use of a plastic substrate instead of a glass substrate for the development of a liquid crystal display, the solvent contained in the liquid crystal alignment agent may be dissolved to dissolve the plastic substrate. The main object of the present invention is to provide a polyphenylene. In the case of an amine or a poly-proline, a liquid crystal alignment agent which solves the above problems caused by using a high boiling point solvent and at least one of the above problems caused by using a solvent having high solubility in a plastic substrate can be solved. A polymer of a constituent component of a liquid crystal alignment agent, a method for producing the polymer, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. [Means for Solving the Problem] In order to solve the above-mentioned problems of the prior art, the present inventors conducted intensive studies and found that the above problems can be solved by using a polymer having a specific phthalic acid vinegar structure, thereby completing the present invention. Specifically, the present invention provides the following liquid crystal alignment polymer, a polymerization method, a liquid crystal alignment film, and a liquid crystal display element. The liquid crystal alignment of the present invention is characterized in that: the polymer containing a phthalate structure is obtained by esterifying a carboxyl group of a proline to form a phthalic acid-containing structure. a group consisting of the structure of the above-mentioned carboxyl group, the structure of the m group, the structure of the above-mentioned base group of 201235384 alkylcycloalkyl ester, and the tertiary alkyl ester structure of the aforementioned mercapto group. At least one of them. According to the liquid crystal alignment agent of the present invention, it is considered that the hydrophobicity of the polymer is improved as compared with the polyaminic acid or its quinone imidized polymer, so that a so-called low boiling point solvent of, for example, 1 80 ° C or less can be used. The above-mentioned conventional problems caused by using a high boiling point solvent such as 1-methyl-2-pyrrolidone (hereinafter referred to as NMP) can be solved. Further, a solvent having a lower solubility in a plastic substrate than NMP or the like can be used, and the above-mentioned conventional problems caused by using a solvent having high solubility to a plastic substrate can be solved. Further, by applying any one of the above various ester structures, after the liquid crystal alignment agent having the above polymer is applied onto the substrate, when the liquid crystal alignment film is formed and heated, the base forming the ester structure is easily removed. Therefore, even if the structure of the phthalate structure is introduced, the function of the liquid crystal alignment film is not deteriorated. In addition, the urethane structure is preferably a acetal structure having a slow-setting group selected from a group not represented by the following formula (1_1), and a slow group formed of a group represented by the following formula (2_ι) At least one of the group consisting of a ketal structure and a ternary vinegar structure of a mercapto group is a structure in which the carboxyl group is esterified. R1 --C—*〇--CH——Ο——R2 (1-1)

II 0 R3 —C-〇-C-〇-R* (2-1)

IIO R4 201235384 (In the above formula (1-1), R1 is an alkyl group having 1 to 20 carbon atoms, R2 is an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, and a carbon number of 3 to 20 An alicyclic group, an aryl group having 6 to 20 carbon atoms or an aryl group having 7 to 20 carbon atoms. In the above formula (2-1), R3 and R4 are an alkyl group having 1 to 12 carbon atoms, and R5 An alkyl group having 1 to 12 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may be substituted by a fluorine atom. In this case, the carboxyl group is added to the liquid crystal alignment film to increase the flexibility of the molecular chain, thereby improving the solubility. In particular, when the carboxyl group is added and the film is crystallized and heated, it is easy to have an ester structure having the structure represented by the above formula (1 -1) as the above-mentioned retardation group, and the above R 2 is an alkane having 1 to 12 carbon atoms. Preferably, the liquid crystal is improved in voltage retention ratio, etc., and according to the present invention, a further polymer obtained by the phthalate structure, the phthalate structure and the ketal ketal At least one of the ester structure and the third level of the above-mentioned rebel. In this case, the group which forms the ester structure with the compound having an unsaturated double bond and the addition thereof is easily detached due to heat, and at the same time, the acetal structure-forming group of the above polymer to the solvent can be improved. When the liquid is detached, it is preferably a structure in which the base of the above-mentioned tyrosine is formed, and the above R1 is a fluorenyl group. The alignment agent further contains a crosslinking agent. Electrical characteristics. Provided is a structure having a structure in which a chiral acid ester structure is obtained by hydrating a buffer base of a valine acid, a structure of a carboxylic acid selected from the carboxyl group, and a structure of a 1-alkylcycloalkylalkyl group of the carboxyl group. The method for producing a polymer in a group is obtained by reacting a ruthenium-imiding polymer to 201235384, which is formed by polyaminic acid or a part thereof by hydrazine imidization. Seeking simplicity in manufacturing. Further, according to the present invention, there is provided a liquid crystal alignment film comprising the liquid crystal alignment agent and a liquid crystal display element comprising the liquid crystal alignment film. [Embodiment] [Formulation for Carrying Out the Invention] The liquid crystal alignment agent of the present invention contains a polymer having a specific phthalate structure. Hereinafter, the liquid crystal alignment agent of the present invention will be described in detail. <Polymer having a phthalate structure> The glutamate structure has a structure in which a carboxyl group carried by valerine is esterified, that is, a structure of -COO-R. Specific examples of the structure include a acetal structure of a carboxyl group, a ketal ester structure of a carboxyl group, an alkylcycloalkyl ester structure of a carboxyl group, and a tertiary alkyl ester structure of a carboxyl group. Hereinafter, the acetal structure of a carboxyl group, the ketal structure of a carboxyl group, the 1-alkylcycloalkyl ester structure of a carboxyl group, and the tertiary-stage structure of a slow-base group will be described in detail. [Acetal ester structure] The group represented by the following formulas (1-1) and (1-2) is exemplified as the group which forms the acetal structure of the several groups. R1 一 —CH — 〇- ~R^ (1-1}

II 0 -C - 0 -CH -(CH2) „1 Π-2) In 201235384 (Formula 0-1), each of R1 and R2 is an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, and a carbon atom. An alicyclic group having 3 to 2 Å, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 2 carbon atoms. In the formula (12), ... is an integer of 2 to 10 0.) The Ri in the formula (1_υ is preferably not substituted by a fluorine atom, preferably a methyl group if it is an alkyl group, a cyclohexyl group if it is an alicyclic group, or a phenyl group if it is an aryl group. If it is an aralkyl group, it is preferably a benzyl group. Further, R is preferably not substituted by a fluorine atom. If it is an alkyl group, it is preferably an alkyl group having a number of slave atoms of 1 to 12, and if it is an alicyclic group, it is preferably. The alicyclic group having 6 to 10 carbon atoms is preferably a phenyl group if it is an aryl group, and a benzyl group or a 2-phenylethyl group if it is an aralkyl group. And nl, preferably 3 or 4. methoxycarbonyl, n-butoxyethoxycarbonyl, octyloxyoxycarbonyloxycarbonyloxycarbonyloxycarbonyloxycarbonyloxycarbonyl as the above formula (1 · 1) The base may, for example, be 1 _ ethoxycarbonyl, 1-ethoxyethoxycarbonyl, 丨-n-propoxy ethoxy 1 primary propoxy ethoxycarbonyl, "isopropoxyethoxycarbonyl, 1-ylethoxycarbonyl, b-isobutoxyethoxycarbonyl , 1-second-butoxybutyryl, tert-butoxyethoxyxy, b-n-pentyl ethoxy 1_n-toxyethoxycarbonyl, "n-heptyloxyethoxycarbonyl," Ortho-ethoxy Ik-based 1-n-decyloxyethoxy group, fluorenyl methoxy-ethyl 1-n-tetradecyloxyethyl 1-n-hexadecane oxy-ethyl 1-n-octadecyloxy-ethyl 1-n-di Decyloxy B, 1-n-decyl-alkoxyethoxycarbonyl, b-dodecyloxyethyl, 1-n-dodecyloxyethoxycarbonyl, 1-n-pentadecanyloxyethoxycarbonyl a branched structure of ruthenium-n-heptadecyloxyethoxycarbonyl, 1-n-nonadecanyloxyethoxycarbonyl, etc.; -10- 201235384-pentyloxyethoxycarbonyl, 1-cyclohexyloxy Ethoxycarbonyl, κ-decyloxyethoxycarbonyl, decyloxyethoxycarbonyl, (cyclohexyl) (f-glycine) methoxym-, (cyclohexyl)(ethoxy)methoxyl (cyclohexyl)(n-propaneoxy)methoxycarbonyl, (cyclohexyl)(isopropoxy)methoxy An alicyclic structure of a carbonyl (hexyl) (% hexyloxy) methoxycarbonyl group; phenoxyethoxycarbonyl, hydrazine-(1-naphthyloxy)ethoxycarbonyl, hydrazine-benzyloxy ethoxy a benzyloxy ethoxyethoxy group, (cyclohexyl)(phenoxy)methoxymethyl, (cyclohexyl)(foxy)methoxycarbonyl, (phenyl) (methoxy) ) methoxy methoxy, (phenyl) (ethoxy) methoxycarbonyl, (phenyl phenyl propyl) methoxycarbonyl, (phenyl) (isopropoxy) methoxycarbonyl (phenyl)(cyclohexyloxy)methoxymethyl, (phenyl)(phenoxy)methoxycarbonyl' (stupyl)(oxy)oxymethyl, (nodal) (Methoxy)methoxybenzyldi(n- ethoxy)f-oxycarbonyl, (nodal) (n-propoxy)methoxy 'large earth (benzyl) (isopropoxy) A Oxycarbonylcarbonyl '(benzyl)(cyclohexyloxy)methoxymethyl, (nodal) (phenoxy)methoxypropyl, (nodal) (oxy)methoxycarbonyl, etc. Aromatic ring structure. Further, examples of the group represented by the above formula (1-2) include, for example, a tetrahydrofuranyloxycarbonyl group, a ditetrahydropyranyloxy group, and the like. [Vinyl Ester Structure] The group represented by the following formulas (2-1) to (2-3) is exemplified as the group forming the ketal ester structure of the carboxyl group. -11- 201235384 R3 (2-1)

c 0 I j|—°—C-〇—Re O R4

(2-2) C--〇

II o

(2-3) (In the formula (2-1), R3 is a halogen atom which can be substituted by a fluorine atom, and R4 and R5 each are a carbon atom number 1 to 12 which can be substituted by a fluorine atom. An alicyclic group having 3 to 2 carbon atoms, an aryl group having 6 to 2 carbon atoms or an aralkyl group having 7 to 2 carbon atoms. In the formula (2·2), R6 is acceptable. An alkyl group having a carbon number of 丨~12 substituted by a gas atom, "is an integer of 2 to 8. In the formula (2-3), "R7 is an alkyl group having a carbon atom which can be substituted by a fluorine atom", n3 An integer of 2 to 8 is selected.) R3 of the above formula (2-1) is preferably not substituted by a fluorine atom, and preferably has a methyl group. Further, R4 is preferably not substituted by a fluorine atom, if decane The base is preferably a methyl group, and if it is an alicyclic group, the cyclohexyl group is preferably an aryl group, preferably a phenyl group, and if it is an aralkyl group, it is preferably a benzyl group, and the 'R is preferably not. The fluorine atom is substituted, and if it is a burnt group, the alkyl group having a reverse atomic number of 1 to 12 is preferably an alicyclic group if it is an alicyclic group: an alicyclic group having a number of 6 to 1 Å, if it is an aryl group, Preferably, it is a phenyl group, and if the anthracene group is a group, it is preferably a node group or 2_ Base group -12- 201235384 As the base of the rule 6 in the above formula (2-2), preferably 112 is preferably 3 or 4. Soil. Further 'as the above formula (2-3) The alkyl group is preferably 113 or 3 or 4. Soil. Further, examples of the group represented by the above formula (2-1) include a methoxyethoxycarbonyl group and a fluorenyl-methyl small ethoxy group. Ethoxycarbonyl fluorenyl-fluorenyl-1-n-propoxy ethoxymethyl, κ-mercapto-l-propyloxyethyl ketone 1-methyl-1-methyl-1-isopropoxy ethoxycarbonyl, methyl n-Butyl, carboxy, Ια 1-methylisoisobutoxyethoxycarbonyl, L methyl]•di: ethyl hydrazine carbonyloxycarbonyl, 1-mercapto-1-tertiary butoxyethoxycarbonyl, ^ Methoxy ethoxyethoxycarbonyl, 1-indenyl-n-n-hexyloxyethoxycarbonyl, n-heptyloxyethoxycarbonyl, 1-methyl-i-n-octyloxy _ _ 乳1-carbamate--n-decyloxyethoxycarbonyl, N-methyl-n-decyloxy, 1-mercapto-1-n-undecyloxyethoxycarbonyl, "methyl small n-doctyl Ethoxycarbonyl, 1-methyl_1_n-tridecyloxyethylene 4-vano-rolled carbonyl, 1-methyl-1-n-tetradecyloxyethoxycarbonyl , ^methyl-Buzhen, 1 · * gray * gas ethoxy group '1-mercapto-1-n-hexadecaneoxy ethoxycarbonyl 'L A is a seven-sodium alkoxy ethoxy group, 1-methyl-1-n- 18 sylvestre oxime oxyethoxycarbonyl, 1-mercapto-1-n-nonadecanyloxyethoxycarbonyl, 丨_methyl _ soil 1 ***** Branched structure of ethoxycarbonyl, etc.; 1-fluorenyl-1-cyclopentyloxyethoxycarbonyl, 1-methyl-indole-cyclohexyloxyethoxycarbonyl, 1-methyl-1-norborn Oxyethoxycarbonyl, 1-f-based ethoxycarbonyl, 1-cyclohexyl-1-methoxyethoxycarbonyl, oxime-cyclohexyl methoxyethoxycarbonyl, 1-cyclohexyl-1 -positive An alicyclic structure of oxyethoxylated, fluorenyl-1-isopropoxyethoxycarbonyl, 1-cyclohexyl-1-cyclohexyloxyethoxy; Mintu-13- 201235384 1 -mercapto-1-phenoxyethoxycarbonyl, 1-methyl-1-(1-naphthalenyloxy)ethoxylated, 1-methyl-1-benzyloxyethoxycarbonyl, diphenyl-benzene Ethoxyethoxymethyl, 1-cyclohexyl-1 phenoxyethoxycarbonyl, 1-cyclohexyl-indole-benzyloxyethoxycarbonyl, 1-phenyl-indole-methoxyethoxycarbonyl,丨_Phenyl-indole _ethoxy ethoxycarbonyl, 1_丨-丨-n-propoxyethoxycarbonyl, 丨-phenyl-^isopropoxyethoxycarbonyl, phenyl-indole-cyclohexyloxyethoxycarbonyl, hydrazine-phenyl-1-phenyloxy Ethyloxycarbonyl, 1-phenyl-1-benzyloxyethoxycarbonyl, 丨-benzyl-1-methoxyethoxycarbonyl, 1-benzyl-1-ethoxyethoxycarbonyl,;- Benzyl-1·n-propoxyethoxycarbonyl, 1-benzyl-1-isopropoxyethoxycarbonyl, 1-benzyl-1-cyclohexyloxycarbonyl, benzyl-1-phenoxy An aromatic ring structure of an ethoxycarbonyl group, a 1-aryl-1-benzyloxyethoxycarbonyl group or the like. The group represented by the above formula (2-2) includes, for example, 2-(2-methyltetrahydrofuranyl)oxycarbonyl group, 2-(2-indenyltetrahydro-β-mercapto)oxy group. Kewei Ke et al. The group represented by the above formula (2-3) may, for example, be a 1-methoxycyclopentyloxycarbonyl group or a 1-methoxycyclohexyloxycarbonyl group. Π-alkylcycloalkyl ester structure] The group represented by the following formula (3) can be mentioned as a group which forms a 1-alkylcycloalkyl ester structure of a mercapto group.

R8 in the number of carbon atoms 1 to 1 2 substituted by a fluorine atom is not substituted by a fluorine atom, specifically, an alkyl group of 10. Further, it is preferable that η4 is 3 or 4. -14 - 201235384

Examples of the A oxycarbonyl group and the 1-methylcyclobutyl decano group represented by the above formula (3) include, for example, a fluorenylcyclohexyloxycarbonyl group, a anaerobic 1-methylcyclopentyloxycarbonyl group, and 1 -methylmercaptocyclocarbonylcarbonyl/cycloheptyloxycarbonyl, "cyclooctyloxycarbonyl, hydrazino-ethylcyclobutane = methylcyclodecyloxy, 1-ethylcyclopropoxyoxyl Ethyl di-ethylcyclopentyloxy, 1-ethylcyclohexyl fluorenyl di:diyl, 1-ethylcyclooctyloxy, rethyl, i-isopropyl Cyclobutanyl m, κ (iso)propylcyclopropoxylated propylcyclohexyloxyhydrazone A pentyloxycarbonyl, 1-(cyclooctyloxy, K(4) propyl (4) propylcycloheptaoxy Base, W) propyl group] (4) butyl 2 oxirane group, W isopropyl) propyl ring oxime i-(iso)butyl ring (iso)butylcyclobutoxy group, base,) Butyl ring oxime; = oxydiyl group =

(,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Bu (4) mercaptocarbonyl, 1 (iso)? ', earth oxygen base, b (iso)pentyl ring oxime oxygen (9) hexapropyloxy group, "(iso)hexylcyclobutoxymethyl, oximeoxy, ketohexylcyclohexyloxy a few groups, a hetero group, a fluorenyl group, a (iso)hexylcyclooctyloxy group, a hexyl hexyl ring, a hexylcyclodecyloxy group, an (iso)heptylcyclopropane (tetra)isoheptyl group环...基! ( = . 屄丞 庚 氧 氧 、 w 庚 庚 庚 r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r , (iso)octylcyclobutoxycarbonyl, -15- 201235384 -(iso)octylcyclopentyloxy, 丨_(iso)octylcyclohexylcycloheptyloxycarbonyl, w iso)octyl Cyclooctyloxycarbonyl oxime oxycarbonyl, iota-(iso)octylcyclooxiranyloxycarbonyl, and the like. [Tertiary alkyl ester structure] A tertiary alkyl group as a tertiary alkyl ester structure forming a carboxyl group may be substituted by a fluorine atom, but it is preferred that the carbon number of the tertiary alkyl group is preferably produced as a group forming a tertiary alkyl ester structure, a butoxycarbonyl 'tertiary pentyloxycarbonyl group, a tertiary hexyloxycarbonyl group, a secondary octyloxycarbonyl group, a tertiary fluorenyloxycarbonyl group, a tertiary undecylene carbonyl group' The dialkoxycarbonyl group or the like having at least one of a polymerized oxime structure having a phthalate structure, a hydrazine structure of the hydrazine structure, and a structure of the above-mentioned sulfhydryl group. The above polymer may be one having an ester group selected from only one type in the structure and structure of the above-mentioned 1-alkylcycloalkyl ester structure of the above-mentioned acetal ester structure, so that the ester structure is selected from a plurality of types. At least one of a plurality of types of ester structures having a plurality of types selected from a plurality of ester structures may be a single repeating unit or a plurality of repeating units having a predetermined type of repeating unit. In view of the above, an ester structure of the type selected from the above-mentioned ketal ester structure and the above 1-alkylcycloalkyl ester-based ester structure. a dioxol group, a 1-(iso)I, an anthracene-(iso)octyl ring group, which is substituted with no gas atom to 4 to 1 2 〇 to enumerate, for example, a tertiary group, a tertiary heptane The oxime group and the oxime group may contain the above-mentioned acetal cycloalkyl ester structure and ester structure, and the above-mentioned substance which shrinks the above-mentioned tertiary alkyl hydrazine, and may also be a substance or an ester structure. . Types of structures, different structures. It is preferable to have only one acetal ester structure, the above structure, and the above-mentioned tertiary combustion -16 to 201235384 as the ester structure of the above polymer, and it is preferably any one of the following 1 to 3. 1. An acetal structure of a carboxyl group formed by the group represented by the above formula (1-1) and R1 is an alkyl group having 1 to 2 carbon atoms, and R2 is a carbon atom which may be substituted by a fluorine atom. An ester structure of an alkyl group of -20, an alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 2 carbon atoms; -1) a ketal ester structure of a carboxyl group formed by a group and each of R3 and R4 is an alkyl group having a carbon number of 12, and R5 is an alkyl group having a carbon number of 丨~丨2 which may be substituted by a fluorine atom, An alicyclic group having 3 to 2 Å carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 2 carbon atoms; 3. A tertiary alkyl ester structure of a carboxyl group in a reverse species In the case where the carboxyl group is added to form an ester structure, the base is easily detached when heated by forming a liquid crystal alignment film, and the flexibility of the molecular chain can be improved, thereby improving the solubility of the polymer in a solvent. - On the 8th day, the 叮 叮 叮 匆 匆 匆 酝 酝 酝 酝 酝 酝 酝 酝 酝 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为The ester structure which is decomposed to be less than 1 50 C and converted into a proline structure. As the above-mentioned polyester, the ketal ester structure and the above-mentioned three-stage vinegar structure are each More preferably, in the case of the above-described ruthenium-reducing structure, it is preferable that the thiol group represented by the above formula (1) is a structure in which R 2 is a carbon atom (4). -17- 201235384 It is more preferable that R2 is a structure of a carbon group having 4 to 6 carbon atoms. Specifically, 1-n-butoxyethoxycarbonyl, 丨-n-pentyloxyethoxy is preferred. Carbonyl group or h-hexyloxyethoxycarbonyl group. In the case of the above ketal ester structure, it is preferred that the above-mentioned formula (2-1) wherein R3 and R4 are a methyl group and R5 is a carbon atom 丨~ Further, it is more preferable that R5 is a structure of an alkyl group having 4 to 6 carbon atoms. Specifically, it is preferably a methyl group-丨-n-butoxy group. Oxycarbonyl, hydrazine-methyl-1-n-pentyloxyethoxycarbonyl or hydrazine-methyl-hydrazine-n-hexyloxyethoxycarbonyl. In the case of the above tertiary alkyl ester structure, it is preferably a tertiary butyl group. Oxycarbonyl group The above-described glutamate structure is specifically represented by the following formula (Ae).

/ \ /R 丨Ra ~^-HNOC^ \〇nh-Rb (Ae) (In the above formula, 'Ra is a tetravalent organic group derived from tetracarboxylic dianhydride, and Rb is a divalent organic group derived from a monoamine. , R is a acetal structure of a carboxyl group, a ketal ester structure of a carboxyl group, a 丨-alkylcycloalkyl ester structure of a carboxyl group or a tertiary alkyl ester structure of a carboxyl group, and R1 is a carboxyl group, a acetal structure of a carboxyl group, and a carboxyl group. The condensed ester structure, the i-alkylcycloalkyl ester structure of the carboxyl group or the secondary alkyl group of the carboxyl group || structure.) Λ is represented by the tetravalent organic group represented by Ra in the above formula (Ae) and 2^ represented by ruthenium The t-group 'specifically' may be exemplified by an aliphatic chain-like nicotyl group, an alicyclic nicotyl group, an aromatic hydrocarbon group or a heterocyclic group, respectively. These groups may be substituted. Alternatively, these groups may be directly or by a prescribed combination. A polycyclic compound group formed by interconnecting crosslinking groups. -18- 201235384 As a solvent having a low solubility to a plastic substrate such as NMP or a solvent having a low boiling point, in the above formula (Ae), R is a carboxyl group acetal in terms of improving the solubility of the polymer. Any one of an ester structure, a ketal vinegar L structure of a carboxyl group, a structure of a thiol group, a structure of a thiol group, and a structure of a tertiary sulphuric acid vinegar. These various ester structures are as already explained. As the polymer having a phthalate structure, all of the repeating units may have a phthalate structure, or a part of the repeating unit may be a phthalate structure. When a part of the repeating unit is a phthalate structure, the remaining repeating unit may be a proline structure or a structure in which the proline structure is imidized. Further, as the remaining repeating unit, a repeating unit having a proline structure may be a repeating unit having a ruthenium iodide structure. <Manufacturing method of polymer having a phthalate structure> A polymer having a phthalate structure can be produced by esterifying at least a part of carboxyl groups of (a) polyglycine. (b) Alternatively, it may be produced by subjecting a thiol imidized polymer formed by partial imidization of polyamic acid to a thiol group. The following is a description of a method for producing a polyaminic acid and a partially ruthenium-imidized polymer. Further, a specific example of the tetracarboxylic dianhydride described below corresponds to a specific example of the tetrabasic acid dianhydride of the tetravalent organic group represented by Ra in the above formula (Ae), and the diamine of the following description Specific examples correspond to specific examples of the divalent organic group-derived diamine represented by Rb in the above formula (Ae). -19- 201235384 [Tetracarboxylic dianhydride] Examples of the tetrazoic acid dianhydride used for & polyarginic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic Tetracarboxylic acid di if and so on. Specific examples of the various tetracarboxylic dianhydrides include, for example, butane tetracarboxylic dianhydride; and the alicyclic tetracarboxylic dianhydride; for example, Alkane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, hexahydro-5-(tetrahydro-2,5-di-sideoxy-3-trifuryl)-naphthofuran • 1 ,3-dione, 1,3,3巳,4,5,915-hexahydro-8-methyl_5_(tetrahydro-2,5-di-oxo-3-furoyl)-naphtho[^^ Furosemide...diketone~^oxabicyclo[3.2.1]octane-2,4·dione_6_ spiro_3,_(tetrahydrofuran-2,5,dione), 5_(2,5-di Side oxytetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane_2:3,5:6 _ dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane·2,4,6,8-dianhydride, 4,9-dioxatricyclo[5.3.1.02'6] Undecane_3,5,8,1〇-tetraketone, etc.; the aromatic private tetracarboxylic acid monoanhydride may, for example, be pyromellitic dianhydride; in addition, it is also possible to use 曰本特开20 10-97 1 88 The tetra-acid dianhydride described in the number. As the tetracarboxylic dianhydride for synthesizing polyglycolic acid, it is preferable that these materials contain a substance containing an alicyclic tetracarboxylic dianhydride, and more preferably a 2,3,5·tricyclopentane ring. A substance containing acetic acid di-if or 1,2,3,4-cyclobutane for four ms 夂-hepatic, particularly preferably a substance containing two needles of 2,3,5•three reciprocal thioglycolic acid. -20- 201235384 As the tetrahedoic acid dianhydride for synthesizing the aforementioned polyamic acid, it is preferable to contain 1 Torr of the total of the tetracarboxylic dianhydride. /. The above, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 12,3,4-cyclobutane tetracarboxylic dianhydride of 2% by mole or more is most preferably only 2, A substance consisting of 3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride. [Diamine] Examples of the diamine used for the synthesis of poly-proline include, for example, a diazonic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organic hydrazine as specific examples of these diamines. Examples of the aliphatic diamine include m-xylylenediamine, 1,3-propylenediamine, tetradecyldiamine, pentadecyldiamine, hexamethylenediamine, and the like; the alicyclic diamine can be used. For example, 1,4-diaminocyclohexane, 4,4,- fluorenyl bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, etc.; For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4·-diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 1,5-diamino group Naphthalene, 2,2'-dimethyl-4,4,-diaminobiphenyl, 4,4,-diamino-2,2·-bis(trifluoromethyl)biphenyl, 2,7_ Diamino hydrazine, 4,4,-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminobenzene) , 2, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4,- (p-phenylene isopropyl) bis(benzene ), 4,4'-(m-phenylenediisopropyl)bis(aniline), iota,4·bis(4·aminophenoxy)benzene, 4,4′-bis(4-aminophenoxyl) Biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diamino Carbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-21- 201235384 -3,6-diaminocarbazole, N-phenyl-3,6-diaminoguanidine Azole, n,N'-bis(4.aminophenyl)-benzidine, N,N,-bis(4-aminophenyl)-N,N,-dimethylbenzamine, 1,4 - bis-(4-aminophenyl)-D-desorphin, 3,5-diaminobenzoic acid, eleven alkoxy-2,4-diaminobenzene, tetradecyloxy-2,4_ Diaminobenzene, fifteenth oxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, Dodecyloxy-2,5-diaminobenzene, tetradecyloxy 2,5-diamino stupid, fifteen-epoxy 2,5-diaminobenzene, ten/, oxy Base-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy_3,5 _Diamine stupid, cholesteryloxy-2,4-diaminobenzene Bile dilute oxy 2,4-diamino stupid, 3,5-diaminobenzoic acid choline, 3,5-diamino quesuccinate, 3,5 -1 Aminobenzoic acid wool sulphate, 3,6-bis(4-aminobenzyloxy)cholane, 3,6-bis(4-aminophenoxy)cholestane, 4_ (4,_Tris-methoxyphenoxy)cyclohexyl_3,5-diaminobenzoate, 4-(4,trifluoromethylbenzyloxy)cyclohexyl-3, 5-_Diamine-based benzoate, 丨^· bis(4-((aminophenyl)indenyl)phenyl)_4•butylcyclohexane, hydrazine, bis (4_((aminophenyl) )methyl)phenyl)_4_heptylcyclohexane, 丨, bis-diaminophenoxy) fluorenyl) phenyl)-4-heptylcyclohexane, hydrazine, hydrazine-bis (4_(( Aminophenyl) fluorenyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine , 3_Aminobenzylamine, i-^4·diaminophenyl)Peptin-4-carboxylic acid '4·(glyphosate-4-yl)benzene-l3-diamine, 1,3-double ( N-(4-aminophenyl)piperidinyl)propane, α-amino _ω_aminophenyl

Cc^2c+1 alkylene and a compound represented by the following formula (Α-1) Η2Νχλ=\ (Α-1) L V-X'-R'-XII Η2Ν^__ff -22- 201235384

χ and X are each a single bond, *_〇_, *_c〇〇_4 *-0 (:0-(where 罄"* L j < " bond is combined with diaminophenyl or R1 R, is an early bond, a methylene group or an alkylene group having 2 or 3 carbon atoms, a is 〇 or 1 b is an integer of 0 to 2 'C is an integer of 1 to 20, wherein a and b are different 〇 'X, X11 and Ri are not a single bond at the same time); the diaminoorganomethoxy oxane can be exemplified by, for example, 1,3-bis(3-aminopropyl)-tetramethyl diazepine 焓#. Here, the diamine of the Japanese Patent Laid-Open No. 20 10-971 88 can also be used.乍 is a divalent group represented by xi_Rl_xn in the above formula (A)), preferably an alkylene group having a methylene group having 2 or 3 carbon atoms, '*_c〇〇_戍*-〇-CH2CH2-o_ (wherein The "*" bond is combined with the diaminophenyl group). Specific examples of the radical CeH2c+1_ include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl n-octyl, n-decyl, n-decyl, and Dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- Alkyl and the like. Preferably, the two amine groups of the diaminophenyl group are at the 2,4-position or the 3,5-position relative to the other groups. Specific examples of the compound represented by the above formula (A-1) include compounds represented by the following formulas 11/(A-1-1) to (eight.1-3).

C5h” O~co° h2n

csH"

C7H15 (A-1-2) (A-1-3) -23- 201235384 [Molecular weight regulator] When 50% of the poly-proline acid is used, it can be used as the above-mentioned tetrahydic acid from January to January. A suitable molecular weight regulator is synthesized into a terminal type: Things. By forming the terminal-modified polymer, it is not damaged. In the case of the effect of the present invention, the liquid crystal alignment agent is further improved in printability (printability). Examples of the molecular weight modifiers include an acid monoanhydride aminated yttrium compound, a monoisocyanate compound, and the like. Examples of such materials: 'acid monoanhydrides, for example, maleic anhydride, phthalic acid isophthalic anhydride, n-decyl succinic anhydride, n-dodecyl amber, positive t ton acid ox, positive a hexamethyl succinic acid needle or the like; the monoaminated S compound may, for example, be an aniline acid compound such as aniline, cyclohexylamine, n-amine amylamine, j-hexylamine, n-heptylamine or n-octylamine. For example, a phenyl isocyanate isocyanate etc. are mentioned. The proportion of the regulator used in the knife is relative to the use of acid dianhydride and diamine. It is preferably 2,000 parts by weight, more preferably 10 parts by weight or less, more preferably 10 parts by weight or less. [Synthesis of polyacrylic acid] The ratio of use of tetracarboxylic acid diamine to provide a synthesis reaction to polylysine is preferably 1 equivalent of an amine group relative to a diamine, and the acid anhydride group of the liver is 0 2 ~2 When 詈^ ^ ^ ο υ·ζ z The proportion of the field weight is better as the ratio of the equivalent. The reaction temperature of polylysine is preferably carried out in an organic solvent at a reaction temperature of preferably _2 (rc~15 (rc, more preferably 〇~gang.c), and the reaction time is preferably (M~24 s. More preferably, it is an oxime for 5 to 12 hours of anhydride and modification, a single specific Sf' anhydride anhydride butyl 9, a naphthalene tetracarboxylate, and a dicarboxylic acid ~1_2 at this time another -24-201235384 here, as an organic solvent Examples of the organic solvent include, for example, an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Examples of the aprotic polar solvent include N-A. Base-2-pyrrolidone, hydrazine, hydrazine-dimercaptoacetamide, hydrazine, hydrazine-dimercaptomethylamine, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylene Examples of the phenol derivative include m-cresol, dinonylphenol, and halogenated phenol; and examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, and propylene glycol; 4-butanediol, triethylene glycol, ethylene glycol monodecyl ether, etc.; the above ketones may, for example, be acetone, A Ethyl ketone, methyl isobutyl ketone, cyclohexanone or the like; examples of the ester include ethyl lactate, butyl lactate, decyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, Ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.; the ether may, for example, be diethyl ether, ethylene glycol decyl ether, ethylene glycol ethyl ether, ethylene glycol- N-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol didecyl ether, two Ethylene glycol diethyl ether, diethylene glycol monodecyl ether, diethylene glycol monoethyl ether, diethylene glycol monodecyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc. The above halogenated hydrocarbon may, for example, be dioxane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, gas benzene, o-dichlorobenzene or the like; -25- 201235384 For example, xylene: isoprene propionate, isoamyl acetonate, and di-, in the organic solvent, it is preferred to use a group consisting of a non-transit agent and a phenol and a derivative thereof ( -organic: one or more organic solvents, or one or more organic solvents selected from the above-mentioned first electric cooling, and one or more selected from the group consisting of alcohol, _, a, sea, and hydrocarbon (second group organic solvent) In the latter case, 'as a second group of organically dissolved examples' is preferably 50% by weight or less, more preferably 4% by weight or less, relative to the first group of organic solvents and the first group organic solvent. The amount of use of the organic solvent (a) is preferably such that the total amount of the 3 dianhydride and the diamine (b) is 0.1 to 50% by weight based on the total amount of the reaction solution. The method can be obtained by dissolving polylysine. The reaction solution can be directly used for the synthesis of a phthalate structure. The poly-proline contained in the reaction solution can also be divided into the structure having the structure of a proline. The synthesis of the polymer, or the purification of the polylysine which is also separated, is used for the synthesis of the lysine compost. The separation and purification of polylysine can be carried out in accordance with the public. [Partially ruthenium iodide polymer] The partially ruthenium iodide polymer can be obtained by subjecting a part of the above synthetic acid to dehydration and ring closure to carry out oxime imidization. In the case, the above-mentioned reaction port formed by dissolving polylysine may be benzene, hydrazine, hydrazine or the like. In the F-type polar solvent, select "the solvent in the machine, the solubilized smoke: the use of the solvent is more than the total amount of the mixture, and the step is better to make the amount of the tetracarboxylic acid (a + b) reach the balance of the polymer of the reaction solution. Polylysamine which can be used in a method of concentrating the structure of the halved structure can be used in the dehydration ring-closure reaction by directly separating the reaction solution from -26 to 201235384 in the dehydration ring-closing reaction. Alternatively, The separation process is used for the dehydration ring closure reaction. For the partially ruthenylated polymer of the present invention, the imidization ratio is 30% or more and 70% or less, more preferably 4% by weight. The ratio of the number of the amidoxime ring structures relative to the polyamidiamine, the ratio of the number of the structure of the ring of the imine ring. Here, the dehydration ring of a part of the amine ring of the sulfimine ring Preferably, the polyhydrazine method or the polylysine is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added as needed, and the latter method is preferably employed. Adding a dehydrating agent to the solution of polyproline In the method of the agent, an acid anhydride such as propionic anhydride or difluoroacetic acid anhydride can be used as the dehydrating agent, and the structure of the chiral acid of polylysine as a dehydrating agent is preferably 1 Torr. A tertiary amine such as pyridinium, monodecylpyridine or triethylamine can be used. The amount of the agent to be used is preferably relative to the de-icing γ·〇ι~ίοmol used as a dehydration ring closure reaction. Each of the use may be enumerated as a solution for use in the synthesis of polylysine. The reaction temperature of the dehydration ring closure reaction is preferably from 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 ° 2 〇~3〇h. The poly-proline polyglycolic acid is preferably the number of acid structures below 60% of the oxime and the percentage of isoindole imilate heating & Method and dehydration ring closure such as acetic acid sf, use amount, phase]. 01~20 mol, tridecyl pyridyl dehydration ring closure catalyst 1 mol for J organic solvent, agent exemplified 0~180., more, More preferably -27- 201235384 into 'or can also be part of the separation After the aminated polymer is refined, it is used for the synthesis of a polymer having a phthalate structure. In this way, a solution containing a solution can be obtained. The reaction solution can be synthesized as a straight polymer or can be reversed. After the separation of the polymer, it can be carried out by a known method. [Esterification reaction] The partial ruthenium imined polymer is reversely coupled to a partial quinone imine contained in a solution having a phthalate structure. A polymer having a phthalate structure of a polymer having a phthalate structure can be obtained by reacting a compound having an unsaturated double bond with a polyamidoxime synthesized as described above or a part of a ruthenium synthesized as described above. The aminated polymer is obtained by an addition reaction. The compound used in the polymer for producing a acetal structure having a carboxyl group may be specifically produced by the above formula (11) or the above formula (1-2). Examples of the compound of the group and the like include vinyl ether such as ethyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether 'n-hexyl vinyl ether, or 3,4-dihydro-211_per pipe. Wait. The compound used in the production of a polymer having a ketal ester structure having a carboxyl group is exemplified by a compound which can form a group specifically exemplified for the above formulas (2) to (23), and examples thereof include, for example, ethyl isopropenyl group. Ether, n-butyl isopropenyl ether, tert-butyl isopropenyl ether, n-hexyl propyl propyl isopropyl isophthalate, and 2-methyl-3-3, dihydro-2H brim. The compound to be used for the production of the polymer having a carboxyl group-containing alkyl group-containing alkyl ester structure may, for example, be a compound which can form a group specifically exemplified for the above formula (3), and examples thereof include, for example, i-methylcyclopropene. L-methylcyclobutene, 1-decylcyclopentene, and the like. • 28-201235384 As a compound which is used for the production of a three-stage alkyl group which is a ketone group, for example, a thiol-alkylene butene which can form a group of the ester structure of the compound and which is specifically listed is exemplified. . For example, the compound may be exemplified as an activator when an addition reaction is carried out. Further, as an acid catalyst, nitric acid, formic acid, oxalic acid, phosphoric acid, sulfonic acid, acidic ion exchange resin, and acid. The catalyst used may be acid catalyzed, and examples thereof include hydrogen acid, sulfuric acid, acetic acid, trifluoroacetic acid, and various various Lewis acids. Preferably, the phosphorus reaction temperature is preferably 0 to 20 (TC, more preferably 2 〇 〜 1 〇〇 t, further preferably 30 to 70. The reaction time is preferably 丨 "hours, more preferably 4 〜 u hours", more preferably 8 to 48 hours. As the above with unsaturated double The amount of the compound to be added is usually 0.1 to 10 moles, preferably 5 moles, more preferably 8 to 12 moles per mole of the structural unit of the molybdenum acid. Viscosity] When the polymer having a phthalate structure is formed into a solution having a concentration of 丨〇% by weight, it preferably has a solution viscosity of 20 to 8 μmPa·s, more preferably 30 to 500 mPa·s. Solution viscosity The solution viscosity (mPa · s) of the above polymer is a polymer solution prepared at a concentration of 10% by weight for a good solvent (for example, butyl acetate or the like) using the polymer, using an E-type rotational viscometer. The value measured at 25 ° C. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is in organic The composition is prepared by dissolving and containing the above polymer having a phthalate structure. -29- monoethyl alcohol monomethyl ketone acetate, diethylene glycol monoethyl diisobutyl hydrazine, isoamyl propionic acid Ethyl ester, isoamyl isobutyrate-based scale, acetate acetate, etc. These solvents may be used alone or in combination of two or more. 201235384 [Organic solution lj ] ,., can be used in liquid crystal alignment agent West? h 士士J令机命佐 A Weitian: The heating temperature at the time of reaching a low temperature, and the low boiling temperature of the low temperature firing below I50t is a preferred example of the organic solvent, which can be hydroxy ,-4-methyl·2_pentanone, ethylene glycol monomethyl ether, emulsified butyl 8 曰 曱 methoxy propionate, ethyl ethoxy propionate methyl ether, G diol ethyl Ether, ethylene glycol-n-propyl ether propyl ether, ethylene glycol, n-butyl ether (butyl cyproterone), diethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl alcohol Ethyl ether, diethylene glycol monodecyl ether, diethylene domain, 'if these organic solvents, compared with γ-butyl-2-pyrrolidine _, etc., for plastic substrates Further, the organic solvent as described above may be exemplified by one or two or more kinds of solvents used in the synthesis reaction of the hydrazine acid. [Additive] The liquid crystal alignment agent of the present invention contains the above-described hydrazine polymerization. The composition may contain other components as needed. Examples of the component include a polymer other than the above-described phthalate structure and at least one epoxy group in the molecule, and a solvent is used for practical purposes. - D, S, acetate, ethylene glycol 'ethylene glycol · isoglycol didecyl ether, diethylene di ethyl ether, ether acetate, ester, diisoamyl, or a mixture of lactones or N _ A low. The compound of the other polymer I is mixed with the acid ester structure in the solvent of the above ((30-201235384 hereinafter referred to as "epoxy compound"), functional decane compound, hydrazine imidization accelerator Wait. [Other Polymers] The above other polymers can be used for the purpose of improving solution properties and electrical properties. Examples of the other polymer include polylysine obtained by reacting tetrazoic acid dianhydride and diamine, and ruthenium iodide polymer (polyimine) formed by dehydration ring closure of the polyglycine. Polyurethane, polyester, polyamine, polyoxyalkylene 'cellulose derivative, polyacetal, polystyrene derivative, poly(styrene) other than the above polymer having a phthalic acid vinegar structure a -phenylbutyleneimine derivative, poly(meth)acrylic acid vinegar or the like. Among these polymers, polyphthalic acid or polyimine, and more preferably polyamine. The above-mentioned tetracarboxylic dianhydride of tetracarboxylic acid dianhydride used as a polymer for synthesizing the above-described phthalate structure can be exemplified as the tetracarboxylic acid di-needle for synthesizing the above poly-plysine or polyimine. For the same substance, it is preferred to use 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 2,3,5-di-hexylcyclopentyl acetic acid dianhydride, and ^, ^^Exo-hexahydro-tetrahydro-2,5-di-oxo_3_furanyl-naphtho[l,2-c]furan-1,3-dione At least one substance selected. As the diamine used for the synthesis of the above polyphosphonic acid or polyimine, it is preferred to use a diamine which can be used in combination as a polymer having a phthalate structure as described above, and is exemplified in the above. At least one selected as the diamine for synthesizing polyamic acid or polyimine, preferably using 4,4'-diaminodiphenylmethane, 4,4,-diaminodiphenyl基-31- 201235384 Ether, 2,2 铤, c....... 吾田坑孔丞_2,4-Diamine",_Aminobenzoic acid and hydrazine, 4-double _( The proportion of at least one selected from the group consisting of 4-aminophenyl)-piper is the ratio of the other polymers to the total of the above-mentioned specific polymer and other polymers. The following phase ten ( 乂 preferably is 90% by weight or less, more preferably 0.1 to 70% by weight, more preferably 0.1 to 30% by weight.

[Epoxy compound J can be used to improve the mechanical strength by using a % oxygen compound as the "parent agent for the ruthenium film" for the liquid crystal alignment film, and it is also possible to increase the mechanical strength. The electric characteristics are such that when the solvent is used as a muse, the heating temperature is low when the organic solvent of the organic solvent is used as the liquid helium alignment agent, and the liquid is adjusted to the liquid crystal voltage. The amination rate is low, and as a result, the oxygen compound is known as a crosslinking agent, but it is known that the addition of a ring can also inhibit the reduction of the number of the ring. In addition, the butyl group can further inhibit the -k π-resistant epoxy compound. It is also possible to use θ 曰: 显示 兀 的 。 。 。 。 。 。 。 。 。 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日Ethylene glycol dimethyl condensate, tripropylene glycol dimethyl ketone glycerol's ether, propylene glycol diglycidyl ether diglycidyl ether, bis-t-pentanediol diglycidyl ether, acetophenone diglycidyl ether, new two Glycidyl ether, triterpenoid, 6-hexanediol Diglycidyl ether, glycerol neopentyl glycol dimethyl: methyl propane triglycidyl ether, 2,2-dibromo oil scale, sense heart, 1 tetraglycidyl group _ di-32- 201235384 toluenediamine, 1 3_簪m double (N,N-diglycidyl N,N,N,,N,-tetrahydrate, ancient and 4 v makeup T base)% hexane, one % &amp; glyceryl _4, 4'-Diaminodiphenyl-glycidyl--the face of χτ χ , fluorenyl, hydrazine, hydrazine-diglycidyl hexane, ν, ν_ dimethyl... keto-aminomethyl nucleus - hexylamine or the like is preferable. The ratio of the weight of 100 parts by weight of the epoxidation unit is preferably 4 parts by weight relative to the lining of the polymer. The following is more preferably 0.1 to 30. Heavy [functional decane compound] By using a functional decane compound agent, it is possible to inhibit the cross-linking of the film as a liquid crystal alignment film at the beginning of the process, thereby suppressing the peeling of the film during the rubbing treatment, and further suppress the liquid 曰2: (It is possible to improve the rubbing resistance. The display of the liquid 曰曰 曰曰 曰曰 曰曰 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 矽 矽 矽 矽 为了 为了 液晶The adhesion to the film and the substrate as a domain functional money compound may, for example, be 3 -aminopropyldimethoxy decane, 3 -amine - ^ _ aminopropyl diethoxy decane, 2-amino group ^ Trimethoxy I, 2-aminopropyltriethoxy, mexin (2_amine:ethyl)-3aminopropyltrimethoxy, n-(2-aminoethyl)amine Propylmethyl decyloxydecane, 3-ureidopropyltrimethoxy decane, 3-ureidopropyltriethoxy s, N ethoxy s-aminopropyltrimethoxydecane, N - ethoxycarbonyl_3_aminopropyltriethoxydecane, N_triethoxycarbenylpropyltriethylenetriamine, ruthenium trimethoxymethoxymethylidenepropyltriethylenetriamine, 10_tridecyloxycarbazinyl-丨4 [triazepam, 1〇-triethoxymethylcarbenyl], 47_triazaindole, 9_trimethoxycarbamido-3 ,6-diazaindolyl acetate, 9-tridecyloxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-33-201235384 3,6 - - murmur-based acetic acid, 〇^ ^ Wenzi 9-trimethoxydecyl-3 6 _ = methyl sulfonate, 9_triple ,6·-nitrogen.N ^ , monoethoxy decyl-3,6-diazepine N-carbyl-3-aminopropyl = methyl ruthenium 二 2 翁 1 曱 1 曱 基矽, N-benzyl _3. Amino-ethoxy ethoxylate; base ^, decyl -3-3-aminopropyltrimethoxy decane, hydrazine # yl-3-aminopropyl dihydrogen hydrazine - Benzyl monoethoxy decane, propylene oxide methyl sulphate, glycidoxymethyl triethoxy ... 2 J J 曱 曱 钱 、, 2 _ _ _ _ _ _ Triethoxyoxyethyl propyloxypropyloxypropyl group = methyl hydrogen 1 3 ' T decyl decane, 3-glycidoxypropyl monooxy decane, and the like. The total amount (10) parts by weight of the blending ratio of these functional anthraquinone compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight. & preferably &lt;wheat-imidation accelerator&gt; As the quinone imidization accelerator, it is preferred to use a low-promoting gelation structure of a polymer having a low-promoting acetamide structure to promote a hardening reaction: a chemical accelerator. By using a low-boiling solvent as a liquid crystal alignment steel = cold back 纟, when the liquid crystal alignment film is formed, the heating temperature is low, and the 'yield imidization rate is low'. The electric characteristics of the voltage retention rate and the like are in February. Lowering, but by adding a low-temperature hydrazine imidization accelerator in advance; &amp; π ^ imidization rate ' suppresses the decrease in electrical characteristics. Further, as the low-temperature curing accelerator, it is preferred to have good solubility in the low boiling point solvent as described above. Specific examples thereof include imidazole, 1,2,4-triazole, benzimidazole, benzimidazole, anthracene, quinoline, isoquinoline, anthraquinone, anthraquinone, quinazoline, oxinolin, and hydrazine. . Nn phenanthrene, benzene wn and different ^, -34- 201235384 benzopyrazine, benzopyrene, benzoquinazoline, phenanthroline, morphine, porphyrin, acridine, 2,2,-bipyridine , 2,4'-bipyridyl, 4,4,-bipyridyl, 2,2,-biquineline, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxyacridine, 2-hydroxyquinoline, 3- Hydroxyquinoline, 4-hydroxyquinoline, 5-hydroxyquinoline, 6-hydroxyquinoline, 7-ylpyridinium, 8 -pyridyl phosphatide, ° amide, amine, isoniazid , Ν, Ν-dimercaptoguanamine, N,N-diethyl sulphonamide, N,N-dimercaptoisonisin, N,N-diethylisonicotin, hydroxynicotinic acid , pyridinate, nicotinic acid ester, isonicotinic acid ester, 2 -&quot; pyridine sulfonamide, 3-pyridine sulfonamide, 4-pyridine sulfonamide, pyridine-2-formaldehyde, nicotinic aldehyde, different Nicotinic aldehyde, 3-nitropyridine, 3-acetoxypyridine, 2-aminopyridine, 3-aminopyridinium, 4-aminopyridine, 2-pyridinecarboxamidine, nicotinic aldoxime, isoniazid Aldehydes, 2-(hydroxymethyl)pyridine, 3(hydroxyindenyl)pyridine, 4-(hydroxymethyl)pyridinium, 2-(hydroxyethyl)D-pyridyl, 3-(hydroxyethyl Pyridine 4-(hydroxyethyl)pyridine, N-oxy-3-hydroxypyridine, N-oxy-4-hydroxypyridine, N-oxy-4-hydroxyquinoline, N-hydroxypyrrole-2,5-dione, N -hydroxyisoindole-1,3-dione, N-hydroxypyrrolidine 2,5-dione, N-hydroxybenzo[de]isoquinoline-1,3-dione, triethylenediamine , hexamethylenetetramine, hydantoin, histidine, uracil, barbituric acid, hydroxypropioniuret, cytosine, N-phenylamine acetic acid, 2-(pyridyl)glycine, color Aminic acid, proline, N-ethylglycine, hippuric acid, Nn than Picolinoyl glycine, N-nicotin glycinate, N-isonialogine, N- Acetyl alanine ' N-benzhydryl cyanoic acid ' N_pyridine fluorenyl (Pic〇nnoyl) alanine, N-nicotin alanine, N-isonicopterin, α-(acetamido) Butyric acid, α-(benzolamido)butyric acid, α-(η ratio, Picolinoyl amino) butyric acid, α-(nicotinyl)butyric acid, α-(isoniazid Amino)butyric acid, N-B-35- 201235384 proline, N-benzoic acid, N- ° pyridine valine, N-nicotinic acid, N-isoniazid Indole hydroxyl Ethyl ketone, trihydroxyacetophenone, dihydroxydibenzophenone, tetrahydroxydibenzophenone, dihydroxybenzophenone, dihydroxybenzamide, trihydroxybenzyl alcohol, trihydroxybenzyl alcohol, Alkoxybenzenediol, alkylhydroxybenzaldehyde, trihydroxybenzaldehyde, nitrophenyldiphenylaniline, dihydroxydiphenylamine, trihydroxydiphenylamine, dihydroxytriphenylamine, three Hydroxytriphenylamine, dihydroxybiphenyl, trihydroxybiphenyldihydroxydiphenyl ether, trihydroxydiphenyl ether, tetradihydroxydiphenyl sulfone, trihydroxydiphenyl fluorene, tetradihydroxydiphenyl Methane, trihydroxydiphenylnonane, dihydroxydiphenylethane, trihydroxydiphenyldiphenylethane, dihydroxydiphenylpropane, trihydroxytetrahydroxydiphenylpropane, dihydroxydiyl Phenylhexafluorophenyl hexafluoropropane, tetrahydroxydiphenyl hexafluoropropanol, dihydroxyerythrone, naphthalenediol, naphthalene triol, ninhydrin, decyl alcohol, decanediol, third alcohol , alcohol, ketone triol, and ketone tetraol. The above quinone imidization accelerator may be used alone or in combination of two or more. When the chemical accelerator is added to the liquid crystal alignment agent, it is 0.1 mole equivalent or more, and the ear equivalent weight is preferably 0.5 to 2.5 mole equivalents per mole of the glutamate structural unit. Picolinoyl acid, benzenetriol, benzophenone, trihydroxyformate, trihydroxycarbamamine, dihydroxy oxy benzenetriol, diol, dihydroxy-hydrazine, hydrazine-diphenylamine , tetrahydroxytriphenylamine, tetrahydroxy, tetrahydroxybiphenyl, phenyldiphenyl ether, hydroxydiphenyl sulfone, tetrahydroxydiphenylethane, tetrapyridyldiphenylpropane, propane , trihydroxy bis, triphenylmethane trinaphthyltetraol, decanediol decyl alcohol, fluorenone 2, the mixing of the low temperature quinone imine polymer may also be preferably 0.2 to 4.0 Mo-36-201235384 [Adjustment of liquid crystal alignment agent] The solid content concentration in the liquid crystal alignment agent (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, and the like. However, it is preferably in the range of 丨~1〇% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described below, and a coating film which is a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film is formed by heating, but when the solid content concentration is less than 1% by weight, When the film thickness of the coating film is too small, a good liquid crystal alignment film cannot be obtained. On the other hand, when the solid content concentration exceeds 1% by weight, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal alignment film; in addition, the adhesion of the liquid crystal alignment agent is difficult. The properties are increased and the coating properties are deteriorated. The particularly preferable solid content concentration range varies depending on the method employed in coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is employed, it is particularly preferable that the solid content concentration is in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, whereby the solution viscosity is in the range of 12 to 50 mPa·s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, whereby the solution viscosity is in the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 丨〇 5 5 Torr, more preferably 20 〜 30 ° C. <Liquid Crystal Alignment Film and Liquid Crystal Display Element> The liquid crystal alignment film of the present invention is formed of the above liquid crystal alignment agent. Further, the liquid crystal display element of the present invention comprises the liquid crystal alignment film. Regarding the mode of action in the liquid crystal display element, it can be applied. [PS type or TN type, STN type, and the vertical alignment type. -37-201235384 The following is a description of the liquid b of the present invention, which is also described in the production of 70 pieces. The method of the present invention can be manufactured by, for example, the following steps (P1) to (P3). [Step (P1): Formation of Coating Film] First, a liquid crystal alignment agent coated with a ruthenium coating was applied to the substrate, and then a coating film was formed on the substrate by a surface of a soil. A TN type, STN type or va type liquid crystal display is produced, and two substrates of the patterned transparent conductive film are formed as a pair, and the t-shaped conductive film forming surface is preferably formed by a plate printing method or a spin coating method. Method, roll coating method | Ρ [3 Β |, + \ / Hemo 卩 brush method respectively coated with the liquid crystal alignment agent of the present invention 'I, by heating each coated surface (preferably by pre-heating ( Forming a coating film by pre-baking and two-stage heating of a baking (post-baking). Here, since the liquid crystal alignment agent of the present invention is excellent in printability, when using a plate printing method as a coating method, It is preferable to exert the excellent effects of the present invention. As the substrate, for example, a glass substrate such as float glass or soda glass can be used. From polyethylene naphthalate, cellulose triacetate (TAC), polyethylene terephthalate, polybutylene phthalate A transparent substrate formed of a plastic such as a diester, a polyether sulfone, a polyamine, a polyimine, a polymethyl methacrylate, a polycarbonate, or a poly(alicyclic olefin). In this case, as the liquid crystal alignment agent of the second invention, since the solubility of the plastic substrate with a low boiling point is mainly lower than that of an organic solvent such as NMP, even if a liquid crystal alignment agent is coated on a transparent substrate made of plastic, It is not easy to dissolve the transparent substrate, and since the heating temperature can be lowered in the post-baking -38-201235384, the deformation of the transparent substrate composed of plastic can be suppressed. In addition, fading of the color filter can be suppressed. As a transparent conductive film disposed on one surface of the substrate, the coffee film consisting of tin oxide (Sn02) (registered by ppG Corporation of the United States) is composed of indium oxide-tin oxide (In2〇3_Sn〇2). For the ITO film or the like, in order to obtain a patterned transparent conductive film, for example, a square formed by a light button after forming a transparent conductive film of a benefit pattern, and a light having a desired pattern when forming a transparent conductive film may be used. The method of the cover, etc. When the coating liquid B is used as an alignment agent, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, it is also possible to apply a functional money compound, functional titanium on the surface of the substrate surface where the coating film is to be formed. Pretreatment of compounds and the like. Then, * the coated surface after the application of the liquid crystal alignment agent is preheated (prebaked) and then formed into a coating film by firing (post baking). The prebaking temperature is preferably 150 C, more preferably 4 Torr to 12 Torr. (:, particularly preferably 4〇~1〇〇π. The prebaking time is preferably 〇·25~10 minutes' more preferably 〇5~5 minutes. The firing (post-baking) temperature is preferably 8〇 ~15 (TC, more preferably 1〇〇~12〇t. The post-baking time is preferably 5~2〇〇 minutes' more preferably 1〇~1〇〇 minutes. Membrane film formed in this way The thickness is preferably G.GG1~ΐμιη', preferably QQ()5~Q5. ^ (Pl-2) On the other hand, when manufacturing a 1PS type liquid crystal display element, the transparency formed by the comb type is set. The liquid crystal alignment agent of the present invention is applied to each of the conductive film formation surface of the substrate of the conductive film and the opposite substrate on which the conductive film is not provided, and then the coating film is formed by heating each coated surface. And a material of the transparent conductive film, a coating method, a heating condition after coating, a pattern of forming a transparent conductive film - 39 - 201235384, a pretreatment of the substrate, and a film thickness of the formed coating film, and the above (P 1- 1) The same. In any of the above (P 1-1) and (P 1-2), after the liquid crystal alignment agent is coated on the substrate, the organic layer is removed. The agent is used to form a coating film as an alignment film. In this case, the crucible can be subjected to a dehydration ring-closure reaction by heating after the formation of the coating film to form a further imidized coating film. [Step (P2): Friction treatment The coating film formed by the above-described method of the TN type, the STN type, or the IPS type is produced by a roll formed by a cloth having the same fiber composition. Thus, the liquid crystal alignment film is applied to the coating film. Nylon, rayon, cotton, the orientation ability of the polishing crystal molecules rubbed in a certain direction, the formation liquid, the processing of the crystal alignment film angle, the photoresist film post-light treatment, and then the enamel in each area crystal display element In the manner described above, the friction is added. [Step (P3): For the liquid to be formed in the pretilt portion of the outer illuminating liquid region of the sputum, the liquid obtained by dispensing the liquid crystal may be applied as described above. For the above liquid crystal alignment film, by changing a portion of the liquid crystal alignment film with a part of violet and performing a 'on the surface of the liquid crystal alignment film, it is different from the previous polishing process. After the treatment of removing the photoresist film, the field of view characteristics can be changed from the different liquid crystal alignment capabilities of the borrowing region. When the VA type liquid crystal display device is manufactured, the coating film can be directly used as a liquid crystal alignment film for processing. Manufacturing] The liquid crystal is disposed between the substrates, and the method of the first method is known as a straight method. First, the two substrates are disposed opposite each other so that each liquid M se* is aligned with the film. To maintain the gap (cell gap), use the sealant to bond the perimeter of the two substrates 'in the surface of the substrate and the poor private, inject and fill the gap in the cell gap of the sealing layer' and then seal Plug injection: y [, external ^ hole can be made into liquid crystal cells. The first method is called ODF (liquid crystal dropping method (0ne

Fill)) method of the method, left-form, 7 + in two crystal substrates of the liquid crystal alignment film on a substrate on a substrate but from the ‘ 疋. The tantalum coating is, for example, an ultraviolet curable seal, and then in the liquid crystal alignment film; ,···, , add liquid crystal on the surface’ and then follow the liquid

Adhere to the film in a way that is affixed to .m ^ L, paste another substrate, and then the substrate

In the case of ultraviolet light irradiation, the straw I can harden the sealant, so that the liquid can be made into a liquid, and the liquid a曰 is preferably reheated in the above manner. The liquid crystal used until the liquid crystal exhibits an isotropic 'degree of water and then slowly cools to room temperature, I removes the alignment during liquid crystal injection. As the retanning agent, for example, an epoxy resin containing a curing agent and an alumina ball as an object can be used. In the nematic liquid crystal and the smectic liquid crystal, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal azo liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane liquid crystal can be used. Liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine monooxo liquid crystal, bicyclooctane liquid crystal, cubic liquid. In addition, in these liquid crystals, a cholesteric liquid crystal such as a gasified cholesterol alcohol phthalic acid vinegar or a cholesteryl carbonate may be added; as a commercial light, a material in the middle portion of the liquid is filled with a crystal cell. The flow interval of the phase, the oxyester liquid crystal crystal, etc., the type of the chiral agent sold in the product name -41-201235384 "C-15", "CB-15; Dioxy...-for use in ferroelectric liquid crystals such as amine-based 2-methylbutyl cinnamic acid vinegar. In the case of sticking a polarizer on the outer surface of the liquid crystal cell, the present invention can be obtained. In the case of the polarizer, a polarizer made of a polarizing film called a "ruthenium film" which is obtained by stretching a vinyl alcohol while holding a vinyl acetate protective film and absorbing a ruthenium film can be used. Or a polarizer composed of the diaphragm itself. The liquid crystal display element of the present invention can be effectively applied to various devices from the 丄 从 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' , car navigation silk, &amp; ^. In the display devices of the Ten Commander, video camera, pDA, digital camera, mobile phone, various monitors, LCD TVs, etc. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. The method for measuring various physical property values is as follows. [Synthesis Example 1] (Synthesis Example of Polylysine) 82 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetrare-acid dianhydride, and 20 g of p-phenylenediamine as a diamine And 98 g of 3,5-diaminobenzimidoxime is dissolved in 800 g of N-methyl-2-° ratio of 11 ketones, and reacted at 6 ° C for 6 hours to obtain 20 A solution of weight % polyaminic acid. The solution viscosity of the polyaminic acid solution (PAA-1) was ijoomPa · s. [Example 1] 50 g of the polyamic acid solution (PAA-1) obtained in the above Synthesis Example 1, 50 g of tetrahydrofuran, 7-6 g of n-butyl vinyl ether, and hydrazine 18 g -42 - 201235384 phosphoric acid were added at 50 ° C Stir for 24 hours. After the reaction, the grass

&amp; Add 100 mL of butyl acetate, wash 5 times with water, then concentrate to 5 〇g, then add butyl acetate to concentrate to 1 〇〇g, to obtain a polymer with glutamic acid gt, gentleman structure A 10% solution of butyl acetate (PAE-1). [Preparation and evaluation of liquid crystal alignment agent] [Example 2] [Preparation of liquid crystal alignment agent] In the polymer-containing (PAE 1 mountain, i) solution obtained in the above Example 1, 'as opposed to the polymer (PAE) -1) 100 parts by mass (solid content) of 20 parts by mass of hydrazine, hydrazine, hydrazine, hydrazine-tetraglycidyl methicone. Add butyl acetate and butyl cyanidin (BC), solvent group, take * butyl salicylate: BC = 40:60 (weight ratio), prepared into a solid content 澧 & ～ ～ The solid content concentration is 4 · 0% by weight of the liquid crystal alignment agent. [Production of Liquid Crystal Display Element] The above-prepared liquid crystal alignment agent was applied onto a transparent conductive film made of an ITO film on one surface of polyethylene naphthalene π having a thickness of 120 μm, using a spin coater. Preheated on a hot plate at 80 ° C; I: baked for 18 minutes and then post-baked in an oven at 150 t for 60 minutes to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 μm. This operation was repeated to obtain a glass substrate with a liquid crystal alignment film on the (two) transparent conductive film. For the above-mentioned pair of polyethylene naphthalate substrates having a liquid crystal alignment film, on each edge of the surface having the liquid crystal alignment film, an epoxy resin coated with an alumina ball having a diameter of 3.5 μm is bonded. The agent is then laminated and crimped in such a manner that the surface of the liquid crystal alignment film is opposed to make the adhesive: Then, a negative -43-201235384 MLC-6608) is injected and filled into the gap of the substrate from the liquid crystal injection port, and then used

In the area, it was evaluated that the liquid crystal alignment was "not good". The liquid crystal alignment property of the VA type liquid crystal display element was "good". ~ X' type liquid crystal (Merck company, M light curing adhesive plugging liquid crystal injection [evaluation of voltage holding rate] For the VA type liquid crystal display element manufactured above, first apply time 60 microseconds, interval 1 67 亳In a manner of applying a voltage of 5 V, it was judged that the voltage holding ratio after the application of the voltage was released to 167 ms was 99%. [Comparative Example 1] Polyacrylic acid solution (PAA-1) was used instead of the polymer (paE). -1) A liquid crystal alignment agent for producing a liquid crystal display element having a solid content concentration of 40.0% by weight of a solid content concentration solution was prepared in accordance with NMP: BC = 40:60 (weight ratio), and the same evaluation as in Example 2 was carried out. The liquid crystal alignment is good, but the VHR is not enough at 96%. [Simple description of the diagram] None. [Key component symbol description] -44-

Claims (1)

201235384 VII. Patent application scope: 1 · A liquid-containing structure will be in the structure of 刖, 2. In the case of the acetal ketal ester of the ester structure, at least the crystal alignment agent' is characterized by: The group of carboxy carboxyl groups of the acetal ester alkyl group is a π π π _ + having a phthalate structure, and the polymer is esterified with a carboxyl group of the amide amine phthalic acid. · The structure of the proline acid g contains # ketal esters of the carboxyl group from the carboxyl group described above, and the name of the carboxyl group. It is composed of at least three species of the carboxyl group. The liquid crystal 3 system of the first aspect of the invention of the mercapto vinegar structure contains a group selected from the group consisting of the following formula (3), wherein the ester structure is formed by a group of the following formula (2-). One of the formed three-stage sputum &amp;&amp; _ structure formed as the carboxyl group is esterified R1, structure '(1-1) 'C-0-CH-Ο- R2 0 R3 〇R4 (In the above formula (1-1), R1 is an alkyl group having a carbon atom number, and the ruler 2 is an alkyl group having a carbon number 丨~" which may be substituted by a fluorine atom, and a carbon number of 3~ An alicyclic group of 20, an aryl group having 6 to 2 carbon atoms or an aromatic group having 7 to 20 carbon atoms; wherein the above formula (^), and the rule 4 are a group of carbon atoms 丨~^ R5 is an alkyl group having 碳~12 carbon atoms, an alicyclic group having 3 to 2 carbon atoms, an aryl group having 6 to 2 carbon atoms or a carbon number of 7 to 20 which may be substituted by a fluorine atom. -45-201235384 The liquid crystal alignment agent of the second aspect of the invention, wherein the aforementioned guanidine ruthenate has an acetal having a carboxyl group formed by the group represented by the above formula (1.冓 is described as a carboxyl group The above-mentioned r1 is a fluorenyl group, and the above R2 is an alkyl group having a carbon number of 丨12. 4. The liquid crystal alignment according to the first aspect of the patent application, which further contains a crosslinking agent. The liquid crystal alignment agent of any one of the above-mentioned claims, wherein the above-mentioned amine amine structure is represented by the following general formula (Ae), CONH--R» \•HNOC (Ae&gt; (In the above formula, Ra * clips white b from the tetravalent organic group of tetracarboxylic dianhydride, R is a divalent organic compound derived from diamine. ^ ^ I baier machine base, again R is a acetal structure of a carboxyl group, a ketal ester of a carboxyl group, 铋e U , a 1-alkylcycloalkyl ester structure of a fluorenyl group or a tertiary alkyl ester structure of a carboxyl group, and κ is a carboxyl group or a carboxyl group. The acetal ester structure 'carboxy ketal ester structure, day, 0 is the 1-alkyl cycloalkyl ester structure of the carboxyl group or the tertiary alkyl ester structure of the carboxyl group.) - a polymer characterized by: Having a phthalate structure, the depleted D醯I s曰 structure is obtained by esterifying a carboxyl group with a valine acid; the aforementioned glutamate structure is a combination of the carboxy group and the carboxy group. The acetal structure of the carboxy group is at least 1 in the group consisting of the ketal ester of the carboxyl group, the oxime-alkylcycloalkyl ester structure of the carboxyl group, and the carboxyl group = core-alkyl ester structure. 46- 201235384 7. The production of a polymer as claimed in claim 6 is achieved by making a compound having an unsaturated double bond. And a liquid crystal alignment film formed by a liquid crystal alignment agent according to any one of the claims. 9. A liquid crystal display element. It has the patented patent crystal alignment film. The method, its trans-proline acid or its reaction and the liquid of the eighth item in items 1 to 5 -47- 201235384 IV. Designated representative map: (1) The designated representative figure is: None. (2) The symbol of the symbol of this representative figure is simple: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0