TW201206978A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, method for preparing retardation film, retardation film, polymer and method for preparing the polymer - Google Patents

Abstract

The present invention provides a liquid crystal alignment film capable of carrying out property of broad view angle, and high quality of display and good property of residual image and burn-in, at the same time; or provides a liquid crystal aligning agent capable of forming liquid crystal alignment film through photo-alignment method, the said liquid crystal alignment film is used for preparing a retardation film that can maintain polarizing statement stably, and the contrast of border of adjacent area having different polarizing statement is excellent. The above-mentioned liquid crystal aligning agent comprises a polymer having structure represented by following formula (1). (in formula(1), R is each independently alkyl of 1 to 4 carbon atoms, hydroxyl, halogen atom or cyano, a is each independently an integer of 0 to 4, ''*'' is a binding bond).

Description

201206978 VI. Description of the Invention: The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a method of forming a retardation film, a retardation film, a polymer, and a method for producing a polymer. More specifically, the liquid crystal alignment agent which is suitable for use in forming a liquid crystal alignment film for use in forming a horizontal electric field type liquid crystal display element or a retardation film by an optical alignment method. [Prior Art] In the liquid crystal display device, a liquid crystal alignment film is provided on the surface of the substrate in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface. The liquid crystal alignment film is usually formed by a method (rubbing method) of rubbing the surface of the organic film formed on the surface of the substrate in a certain direction by a cloth such as nylon. This is also the same in the horizontal electric field type liquid crystal display element. However, when the liquid crystal alignment film is formed by the rubbing treatment, dust or static electricity is easily generated in the rubbing step, and there is a problem that the dust adheres to the surface of the alignment film, which causes a poor display, and has a TFT (Thin Film Transistor). In the case of the substrate of the element, there is also a problem that the circuit of the TFT element is destroyed by the generated static electricity, which causes a decrease in the yield of the product. Therefore, as another means for aligning the liquid crystal in the liquid crystal cell, a radiation-aligned organic film formed on the surface of the substrate is irradiated with polarized or non-polarized radiation, and a light alignment method for imparting liquid crystal alignment energy is proposed (see Patent Documents 1 to 4). . The photo-alignment method does not generate dust or static electricity in the step, and a uniform liquid crystal alignment can be formed. In addition, when irradiating the radiation, by using an appropriate mask ', it is possible to impart a liquid crystal alignment energy only to any region on the organic film or to change the irradiation direction or the polarization axis by multiple radiation. The method and the method using the reticle may also form a region in which the liquid crystal alignment direction is not formed on one organic film. However, the liquid crystal alignment film formed by the photo-alignment method has a desired pretilt angle developability in the shape, but it is pointed out that the formation of the alignment state may be improved over time due to the application of voltage for a long period of time. In addition, as a liquid crystal display element of a liquid crystal display element having a currently known meandering type, an STN (super twisted nematic) type, and a VA (vertical alignment) type, an IPS (in-plane switching) type is also known. A cross-field type liquid crystal device in which an electric field is generated in a direction parallel to the substrate on one side of the pair of substrates arranged in the opposite direction (Patent Documents 5 to 7 and Non-Patent Document 1). It is known that the horizontal electric field display element has a viewing angle property and can be displayed with high quality as compared with a conventional vertical electric field type liquid crystal display element in which an electrode is formed on both substrates and an electric field is generated perpendicularly to the substrate. In the liquid electric field type liquid element, since the liquid crystal molecules respond to electric power only in a direction parallel to the substrate, the refractive index change in the long-axis direction of the liquid crystal molecules does not become a problem. When the viewing angle is changed, the contrast and the display color confirmed by the observer are small. Therefore, it is possible to display with high quality regardless of the angle of view. In order to obtain an advantageous effect, it is advantageous that the dependence of the incident angle of the incident polarized light is small. For the horizontal electric field type liquid crystal display element, it is desirable that the pretilt angle in the initial alignment property is not applied to be small. The direction is taken together to make the same initial initialization, and the TN (twisted liquid crystal FFS (the side forms the electric display, and the liquid crystal is more linear in the straight direction), even if the degree changes, so the time In the case of such a horizontal electric field type liquid crystal display device, when liquid crystal alignment is imparted to the liquid crystal alignment film, in order to avoid the defects of the above rubbing method, it is desirable to use a photoalignment method. However, it can be used in the above photoalignment method. In order to impart photosensitivity to the polymer contained therein, the liquid crystal alignment agent must contain an aromatic structure in a large proportion. However, if a liquid crystal alignment film containing an aromatic structure in a large proportion is used, the pretilt angle is inevitably increased and is eliminated. The above-described advantageous effects of the horizontal electric field type display element. In addition, in the horizontal electric field type liquid crystal display element using the optical alignment method, there is a problem of image sticking and burn-in, and it is desired to improve it. The difference in brightness produced on the screen caused by the change of state over time will be considered by the observer to be burned, and it is not necessary to improve it. As described above, in the horizontal electric field type liquid crystal display element, it is not known that the above advantageous effects can be sufficiently exhibited by the photo-alignment method, and a liquid crystal alignment film which exhibits improved afterimage properties and burn-in properties can be formed. In the liquid crystal display device, it is strongly desired to use a retardation film for the purpose of eliminating the transition of display color development and eliminating the dependence of viewing angle (see Patent Documents 9 and 10). The retardation film is produced by a method using an extension step of a plastic film, a method of curing a polymerizable liquid crystal on a substrate, etc. Among them, a retardation film produced by the latter method can have more complicated optical properties 'in liquid crystal display In the method of hardening a polymerizable liquid crystal, since it is necessary to harden the polymerizable liquid crystal molecules in a state of being aligned with respect to the substrate surface in the direction of the predetermined -6 - 201206978, generally after the liquid crystal alignment film is provided on the surface of the substrate, a method of forming a layer of a polymerizable liquid crystal molecule and hardening it. When the liquid crystal alignment energy is imparted to the film, the optical alignment method is applied to the field. In addition, in recent years, the technique of displaying 3D (three-dimensional) images is popular, and even in the home, it is possible to view 3 A D-Video display is becoming popular. As a display method of a 3D image, for example, Patent Document 17 proposes a method of using polarized glasses having a polarizing plate having a configuration in which a right-eye image and a left-eye image are formed. For images with different polarization states, the right eye and the left eye only see images of their respective polarized states (refer to the patent document Π). The stereo image obtained in this way does not flicker, and the observer wears light and inexpensive polarized glasses, which can be appreciated. A technique for forming a video having a different polarization state of a right-eye image and a left-eye image in one display device as a display device for a home 3D video image is known as follows: Between the pixels, a mosaic-like polarizing layer whose polarization axes are orthogonal to each other is closely attached to the front of one display device, and the observer wears polarized glasses. To observe a stereoscopic image. In the case of the polarizing layer, it is generally considered to be used as a pattern-like retardation film having a micron-order pattern. As a method of producing such a patterned retardation film, for example, Patent Document 12 discloses a method of irradiating a polarizing polymer layer with a polarized light. However, the thermal stability of the photosensitive polymer layer obtained by this technique is insufficient, and the contrast of the boundary between adjacent regions having different polarization states is insufficient. 201206978 In the field of the retardation film, it is desired to provide a material which is excellent in contrast between adjacent regions in which the polarization state can be stably maintained and the polarization state is different. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 12] Japanese Laid-Open Patent Publication No. 2005-49865 [Patent Document 13] JP-A-2010-97188 [Non-Patent Document] [Non-Patent Document 1] "Liq. Cryst.,,, vol. 22, P379 (1996) [Non-Patent Document 2] "UV-curable liquid crystal and its application", Liquid Crystal, Vol. 3, No. 1, 1999, pp 34~42 201206978 [Summary of the Invention] [Problems to be Solved by the Invention] The invention is based on the above problems, and its purpose is to provide A liquid crystal alignment agent which forms a liquid crystal alignment film by a photo-alignment method, and when the liquid crystal alignment film is applied to a liquid crystal display element of a TN type, an STN type or a lateral electric field type, particularly when applied to a horizontal electric field type liquid crystal display element, A wide viewing angle property and a high quality display and good burn-in property are achieved. Another object of the present invention is to provide a liquid crystal alignment agent for forming a liquid crystal alignment film which can be used for manufacturing to stably maintain a polarization state. A phase difference film having excellent contrast between adjacent regions in different states is known. The other objects and advantages of the present invention will be described below. [Means for Solving the Problems] According to the present invention, the above objects and advantages of the present invention are through a liquid crystal. The alignment agent is realized, and the liquid crystal alignment agent comprises a polymer having the following formula (1):

(In the formula (1), R is an alkyl group having a carbon number of 1 to 4, a transradical group, a tooth atom or a cyano group, and a is an integer of 0 to 4, respectively, indicating a linkage;) -9 * 201206978 [Invention Effect] The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film by photo-alignment method, and the liquid crystal alignment film can realize both wide viewing angle properties and high-quality display, especially when used for a horizontal electric field type liquid crystal display element. With good burn-in properties. Therefore, the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal alignment agent simultaneously realizes wide viewing angle properties, high-quality display, and good burn-in property, and is suitable as various liquid crystal display elements such as watches and clocks. It is used for liquid crystal display elements used in display devices such as game machines, word processors, notebook computers, navigation systems, video recorders, PDAs, digital cameras, mobile phones, various monitors, and liquid crystal televisions. Further, the liquid crystal alignment agent of the present invention can also provide a liquid crystal alignment film for producing a phase difference film which is excellent in contrast between adjacent regions in which polarization states are stably maintained in a polarized state. The retardation film produced using the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitably used as a retardation film used in a device for 3D image display. [Embodiment] The liquid crystal alignment agent of the present invention comprises the above formula (1) The polymer of the structure shown below (hereinafter referred to as "structure (1)") (hereinafter referred to as "specific polymer"). <Specific polymer> The R in the above formula (1) is preferably an alkyl group or a halogen atom having 1 to 4 carbon atoms, more preferably a methyl group or a fluorine atom. a is preferably 0 to 2, more preferably 0 or 1. -10- 201206978 The specific polymer in the present invention preferably further has, in addition to the structure (1) as described above, a methylene group or an alkylene group having 2 to 12 carbon atoms (wherein the alkylene group) One or more of a methylene group and a (di)alkylmethylene group at a position other than the terminal of the alkylene group may be an oxygen atom, an ester bond, a divalent alicyclic group having 5 to 10 carbon atoms, or carbon A structure formed by a aryl group having 2 to 24 atoms, a dialkylmethylidene group or a dialkyl decyloxy group having 2 to 10 atoms (hereinafter referred to as "structure (2)") . By further having such a structure, it is possible to impart appropriate flexibility to a liquid crystal alignment film formed of a liquid crystal alignment agent containing the specific polymer, thereby exhibiting good liquid crystal alignment, which is preferable in this respect. In the above, the divalent alicyclic group having 5 to 10 carbon atoms is exemplified by, for example, 1,4-cyclohexylene group; and the above-mentioned aryl group having 6 to 24 carbon atoms is exemplified by 1 , 3-phenylene, 1,4-phenylene, etc.; The dialkyl oxalate group having 2 to 10 sand atoms, for example, a group represented by the following formula:

Si Ο--Si— * ^b^2b+1 /c CbH2b+i (in the above formula, b is an integer, c is an integer from 1 to 9, and represents a linkage) -11- 201206978 as by 1, 2-stretching 10-stretching base, structure, etc. Specific examples of the structure (2) include ethyl, 1,4-tert-butyl, anthracene, 6-exexyl, 1,8-exenyl, 1, 1, 1- 2-. The group formed by the group represented by the following formula: *CH2〇(CH2)2〇CH2—1_*—CH20(CH2)40CH2— 1 *CH2〇(CH2)6〇CH2~ 1 ch3 I 3 -ch2och2- C—ch2och2-ch3 * —ch2o-ch—ch2och2-ch3 * ——ch2o(ch2)2o(ch2)2och2— 1 *-CH2O—C—(CH2)4~C—OCH2~ 1 〇° * —CH2〇 1~( οοη2~ 1

-12- 1 _ch2o-(^—y—c—och2— 1 0 0 201206978 —ch2o-

O CH· CH·

C-och2- O ch3 ch3 a CH2〇(CH2)3_ 宁卜.一宁卜(CH2)3〇CH2- ch3 ch3 -ch2o och2- --0CH2~ -CH, -ch2〇A } \ /-〇ch2-

CH

-CH

/-〇ch2- CH.

-och2— (In the above formula, the connection key is indicated). The structure (2) in the present invention is preferably an alkylene group having 2 to 12 carbon atoms (wherein the alkylene group is a methylene group at a position other than the terminal of the alkylene group and (2) One or more of the alkylmethylene groups may be formed by an oxygen atom, an ester bond, and a divalent alicyclic group having 5 to 1 ring of carbon atoms. -13- 201206978 The content of the above structure (1) in a specific polymer is preferably 5xl 〇 4 to 4xl (T3mol/g, more preferably lxl (r3 to 3.5xl (r3mol/g' and more preferably l_5xl) 〇_3~3xl (T3mol/g. The content of the above structure (2) in the specific polymer is preferably 6xl (T3mol/g or less, more preferably lxl0·3 〜6χ10·3πιο1/8') and more preferably 1.5xlO-3~4xl (T3mol/g ° The structures (1) and (2) in the specific polymer may be located at more than one position selected from the main chain, side chain and end of the polymer' but from the formed liquid crystal The aspect of the alignment film having a small pretilt angle is preferably located in the main chain of the polymer. As the main skeleton of the specific polymer in the present invention, for example, polyorganooxane, polylysine, and polyimine may be mentioned. , polyglycolate, polyester, polyamine, polyoxyalkylene, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, a poly(meth) acrylate, a reactant of a polyfunctional carboxylic acid and a polyfunctional epoxy compound, etc., among which 'preferably a polyfunctional carboxylic acid and a plurality of officials The reactant of the epoxy compound. The reactant of the polyfunctional carboxylic acid and the polyfunctional epoxy compound as the specific polymer in the present invention' may be Μ iii 壬彳 只要 只要It is preferable to include a diepoxy compound oxygen compound and a polyfunctional carboxy group containing a dicarboxylic acid having the structure (1) from the viewpoints of the simplicity of the production method and the ease of separation and purification of a specific polymer valley. The reaction product of an acid. -14-201206978 Hereinafter, a method for producing a specific polymer which is preferable in the present invention will be described in detail. [Polyfunctional epoxy compound] A polyfunctional compound used for producing a specific polymer preferred in the present invention. The epoxy compound comprises a diepoxide compound. The diepoxide compound is a compound having two epoxy groups, which may be a compound in which two epoxy groups are bonded, or may be in addition to two epoxy groups. Further having the compound of the structure (2) as described above. The diepoxide compound further has a structure (2) as described above by using two epoxy groups. The specific polymer obtained preferably has the structure (2) in addition to the structure (1), and is preferred. Specific examples of the diepoxy compound are compounds in which two epoxy groups are bonded, respectively. A compound represented by the following formula (DE-1); and a compound having the structure (2) as described above in addition to the two epoxy groups, for example, the following formulae (DE_2) to (DE_U), respectively Compounds indicated, etc. -15- 201206978 Δ_Δ ( DE-1 ) ^-(CH2)4-^ ( de·2 ) Λ CH2〇(CH2)4〇CH^ (DE-3 )

9H3 2—C~CH2OCH2'

(DE-4 ) CH2OCH CH3

(DE-5)

CH3 ch3 (DE-6 )

CH2〇(CH2)3~Si-〇-Si-(CH2)3〇CH2' ch3 ch3 ^-CH2〇(CH2)2〇CH2·^ ( DE-9 ) ^CH2OCH2〇CH2OCH2·^ ^-CH20(CH2 2〇(CH2)2〇CH2-^ (DE-11} -16- 201206978 The diepoxy compound may be used singly or in combination of two or more. As the polyfunctional epoxy compound in the present invention, Other polyfunctional epoxy compounds are used together with the above-mentioned diepoxy compound. As other polyfunctional epoxy compounds which can be used herein, it is preferred to have a compound having three or more epoxy groups, more preferably three or four rings. Examples of the oxy group compound include, for example, trimethylolpropane triglycidyl ether, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylenediamine, 1,3. - bis, diglycidylaminomethyl)cyclohexane, >^chuan, >^,:^'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. The ratio of the use of the diepoxy compound in one or more of the "multifunctional epoxy compounds" selected from among them may be used, relative to a total of 1 mol of the polyfunctional epoxy compound. Preferred over 〇.5mol 'greater than 〇.5mol more excellent, 0.999mol less, and more preferably greater than 〇.8mol' 0.998mol less, particularly preferably greater than 0.9mol, 0_995mol less. By forming such a use ratio, the effect of the present invention can be impaired', and the heat resistance and light resistance of the electrical properties of the formed liquid crystal alignment film can be further improved. [Polyfunctional carboxylic acid] The polyfunctional teaching acid used in the production of a preferred specific polymer in the present invention is a compound comprising at least one of the above structures (1) and two residues (having the above structure ( The dicarboxylic acid of 1) is hereinafter also referred to simply as "dicarboxylic acid"). -17-201206978 Examples of such a dicarboxylic acid include compounds represented by the following formulas (DC-1) to (DC-4), respectively.

The dicarboxylic acid may be used singly or in combination of two or more. As the polyfunctional carboxylic acid in the present invention, other polyfunctional carboxylic acid may be used together with the above monocarboxylic acid. The other polyfunctional phthalic acid which can be used herein is a polyfunctional carboxylic acid having no such structure (丨), preferably a compound having three or more residues, more preferably a compound having three or four carboxyl groups. As such a polyfunctional carboxylic acid, preferred examples thereof include trimellitic acid, pyromellitic acid, 3,5-tris(4-carboxyphenyl)benzene, and I, 2,4-. As the cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid or the like, one or more selected from them can be used. The use ratio of the dicarboxylic acid in the polyfunctional carboxylic acid is preferably more than 0.1 mol, more preferably more than 0.5 mol, and more preferably 〇 999 mol or less, more preferably more than 〇, based on the total of 1 mol of the polyfunctional epoxy compound. 8 m〇1 and 0.998 mol or less, particularly preferably more than 〇9 m〇1 and 〇995 m〇1 or less. By using -18-201206978 to form such a use ratio, the effect of the present invention can be impaired, and the heat resistance and light resistance of an electric property can be improved. [Method for Producing Specific Polymer] The specific polymer preferred in the present invention can be obtained by preferably dissolving the above-mentioned functional epoxy compound and polyfunctional carboxylic acid in an appropriate organic solvent. The ratio of the polyfunctional epoxy compound and the polyorganism when the specific polymer is produced is relative to 1 mol of the polyfunctional epoxy compound, and the amount of the polyfunctional compound is preferably 0.8 to 1.2 mol, more preferably 〇.9 to 1.1 mol. . Examples of the organic solvent which can be used in the reaction of the polyfunctional epoxy compound with the polyfunctional carboxylic acid include aliphatic hydrocarbons, phenolic solvent esters, ketones, and aprotic polar solvents. Among them, a phenolic solvent or an aprotic agent is preferred from the viewpoint of solubility of the raw material and the like. Specific examples of the above-mentioned preferred organic solvent include a phenolic solvent, and examples thereof include m-cresol, xylenol, and phenylphenol; and examples of the aprotic polar solvent include N-E-pyrrole. Pyridone, N,N-dimethylacetamide, N,N-dimethylformamide dimethylimidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethylmethylphosphonium Triamine and the like. The organic solvent is preferably used in a ratio of 5 or more, more preferably 10 to 50% by weight, based on the solid content concentration (the ratio of the weight of the organic component in the reaction solution to the total weight of the solution). Step by step to improve the multi-agent anti-carboxylic acid carboxylic acid in the use of, ether, and product polar solubility, as phenol, haloin-2-, hydrazine, hydrazine-urea, six solvents in wt% -19- 201206978 The reaction of the functional epoxy compound and the polyfunctional carboxylic acid can be carried out in the presence of a catalyst as needed. As the catalyst, in addition to the organic base, a compound known as a so-called curing accelerator which promotes the reaction between the epoxy compound and the acid anhydride can be used. Examples of the organic base include 1-4 organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; and triethylamine, tri-n-propylamine, and tri-n-butyl A tertiary organic amine such as a base amine, pyridine, 4-dimethylaminopyridine or diazabicycloundecene; a 4-grade organic amine such as tetramethylammonium hydroxide. Among these organic bases, a tertiary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, ruthenium or 4-dimethylaminopyridine is preferred; tetramethylammonium hydroxide is preferred. Such a 4-stage organic amine" as the above-mentioned hardening accelerator' may, for example, be benzylated dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, or cyclohexyldimethylamine a tertiary amine such as triethanolamine; like 2-methylimidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, benzylidene 2-methylimidazole, benzyl-2-phenylimidazole, hydrazine, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)_2-methyl Imidazole, 1-(2-cyanoethyl)-2-n-alkylimidazole, 1-(2-cyanoethyl)-2.phenylimidazole, 1-(2-cyanoethyl)-2 -ethyl_4-methylimidazole, 2-phenylmethyl-5-hydroxymethylimidazole, 2·phenyl·4,5-bis(hydroxymethyl)imidazole, l-(2-cyanoethyl) -2-phenyl-4,5-bis[(2,-cyanoethoxy)methyl]imidate, 1-(2-cyanoethyl)-2-n-undecylimidazole benzene- 20- 201206978 Tri-stearate , 1-(2-cyanoethyl)-2-phenylimidazolium phthalate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole Salt, 2,4·diamino-6-[2'-methylimidazolyl-(1,)]ethyl-s-triterpene, 2,4-diamino-6-(2'-positive Monoalkylimidazolyl)ethyl-s-trin, 2,4-diamino-6-[2,-ethyl-4'-methylimidazolyl-(1')]ethyl-s-three Well, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl_(1' An imidazole compound such as an ethyl-s-tripper isocyanuric acid adduct; an organophosphorus compound such as diphenylphosphine, triphenylphosphine or triphenylphosphite; like benzyl chloride Phenyl money, tetra-n-butyl bromide, methyl triphenyl iron bromide, ethyl triphenyl iron bromide, n-butyl triphenyl bromide, tetraphenyl bromide, iodide Triphenyl sulfonium, ethyl triphenyl sulphate, tetra-n-butyl fluorene, hydrazine-diethylphosphonium dithiosulfate, tetra-n-butyl benzotrifluoride, tetra-n-butyl Scale tetrafluoroborate, tetra-n-butyl quaternary tetraphenylborate a grade 4 scale salt such as a salt or tetraphenylphosphinium tetraphenylborate; a diazabicycloalkene such as 1,8-diazabicyclo[54〇]undecene-7 and its organic acid salt ; organometallic compounds such as zinc octoate, tin octoate, acetoacetate aluminum ruthenium; like desert tetraethylammonium, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butyl chloride a money-like grade 4 salt; a boron compound such as a gasification shed or a triphenyl phthalate; -2 1- 201206978 a metal halide such as zinc chloride or tin chloride; a high melting point dispersion type potential A latent curing accelerator such as a hardening accelerator, a microcapsule latent curing accelerator, or a thermal cationic polymerization latent curing accelerator. The above-mentioned high-melting-point-dispersion latent curing accelerator' may, for example, be an amine addition-promoting accelerator such as dicyanoguanamine or an adduct of an amine and an epoxy resin; and the above-mentioned microcapsule type latent curing Examples of the accelerator include an accelerator formed by coating a surface of a hardening accelerator such as the above-described imidazole compound, an organic phosphorus compound, and a quaternary salt salt, and the like; and the thermal cationic polymerization type latent curing accelerator is exemplified. For example, Lewis acid, Bronsted acid salt, and the like. The use ratio of the above catalyst is preferably 30 parts by weight or less based on 100 parts by weight of the polyfunctional epoxy compound and the polyfunctional carboxylic acid. The reaction of the polyfunctional epoxy compound and the polyfunctional carboxylic acid is preferably carried out at a temperature of from 25 to 200 ° C., more preferably from 40 to 180 ° C, preferably from 1 to 48 hours, more preferably from 1 to 2 4 hours. The terminal of the specific polymer in the present invention may be a carboxyl group or an epoxy group, or may be an epoxy group which is opened by hydrolysis or the like. The particular polymer of the present invention can be used directly to prepare an alignment agent, especially if the terminal is not modified. However, 'at the time of manufacture or after the production of the specific polymer of the present invention', for example, a monocarboxylic acid such as benzoic acid or a monoepoxy compound such as benzyl glycidyl ether is added to react to form a terminally modified specific polymer. For the preparation of an alignment agent. -22-201206978 <Other components> The liquid crystal alignment agent of the present invention contains the above specific polymer as a must-have component, and may contain other components as long as the effects of the present invention are not impaired. Examples of the other component include a polymer having no structure π) (hereinafter referred to as "another polymer") and a compound having at least one epoxy group in the molecule (excluding a specific polymer. Hereinafter, It is called "epoxy compound", a functional decane compound, and the like. [Other Polymers] The above other polymers can be used to further improve the solution properties of the liquid crystal alignment agent of the present invention and the electrical properties of the resulting liquid crystal alignment film. As the other polymer, there is a polymer having no structure (1), preferably from, for example, polyphthalic acid, polyimine, polyorganosiloxane, polyphthalate, polyester, polyamine, Any one selected from the group consisting of cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like may be used. . As the other polymer of the present invention, at least one selected from the group consisting of polyproline and polyimine is preferably used. {Polyamic acid} The above polylysine can be obtained by reacting tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride used for the synthesis of the polyamic acid in the present invention may, for example, be an aliphatic tetraacid dianhydride, an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butyric acid dianhydride; and -23 to 201206978, as the alicyclic tetracarboxylic dianhydride, for example, 1, 2, and 3 are exemplified. , 4-cyclotetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Bis-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 · (tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-(;]furan-1,3-dione, 3-oxabicyclo[3.2.1] Oct-2,4-dione-6-spiro-3'-(tetrahydrofuran.2',5,-dione), 5-(2,5-di-oxytetrahydro-3-furanyl)-3 -methyl-3-cyclohexene-1,2- dianhydride, 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[5.3.1.0''6]undec-3,5 (8,10-tetraketone, etc.), and the like, for example, pyromellitic dianhydride, and the like, and the use of the patent document 13 (Japanese Patent Laid-Open Publication No. Hei 20 1 0-97 1 8 8) Recorded in As the tetracarboxylic dianhydride for synthesizing the above polyamic acid, tetraic acid dianhydride containing alicyclic tetracarboxylic dianhydride is preferable, and more preferably contains 2, 3, 5 - 3 At least one tetracarboxylic dianhydride selected from the group consisting of carboxycyclopentyl acetic acid dianhydride and 1,2,3,4·cyclotetracarboxylic dianhydride, particularly preferably 2,3,5-tricarboxycyclopentyl The tetracarboxylic dianhydride of the acetic acid dianhydride. The tetracarboxylic dianhydride used for the synthesis of the polyamic acid preferably contains 50 mol% or more, more preferably 80 m〇l% or more, based on the total tetracarboxylic dianhydride. , at least one tetraacid dianhydride selected from the group consisting of 3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclotetracarboxylic dianhydride; preferably only 2, 3, 5--24- 201206978 At least one selected from the group consisting of tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclotetracarboxylic dianhydride. As a second for the synthesis of polylysine Examples of the amine include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples thereof are as an aliphatic diamine, and examples thereof include, for example, 1 , M-xylylenediamine, 1,3,propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, etc.; as the alicyclic diamine, for example, 1, 4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-di(aminomethyl)cyclohexane, etc.: As the aromatic diamine, it can be enumerated For example, p-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, :!, 5-diaminonaphthalene, 2, 2' - dimethyl-4,4,-diaminobiphenyl, 4,4,-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diamino fluorene, 4 , 4, diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4,-(p-benzodiazepine Isopropyl) bis(aniline), 4,4,_(m-phenyl-isohexanyl)bis(aniline), 1,4-bis(4.aminophenoxy)benzene, 4,4,-di (4-Aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6 -diamine acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole 'N-benzene -3,6-diaminopurine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'- Dimethylbenzidine, 14-bis(4-aminophenyl)_piped, 3,5_ -25- 201206978 diaminobenzoic acid, cholestyloxy-3,5-diaminobenzene, gall Terpeneoxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diamine Cholesteryl benzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoic acid, 3,6·bis(4-aminobenzene Methoxyoxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5 -diaminobenzoic acid ester, 4-(4'-trifluoromethylbenzylideneoxy)cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-di(4-(( Aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,di(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1 , 1-two (4 -((Aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4) -heptylcyclohexyl)cyclohexane and a compound represented by the following formula (DD;

(In the formula (D-1), X1 is a hospital group having a carbon number of 1 to 3, *_〇·, *<〇〇_ or *-OCO- (wherein, a bond with "*" and two Aminophenyl linkage), m is 0 or 1, η is an integer of 〇~2, and p is an integer of 1 to 20) As the diamine organooxane, for example, 丨, 3 _2 (3 _ Aminopropyl)-tetramethyldioxane or the like, and a diamine described in Patent Document 13 (JP-A-2010-97188). -26- 201206978 The χι in the above formula (D-1) is preferably an alkyl group having a carbon number, *-0 - or *·(: 00- (wherein, a bond with "*," and two Aminophenyl linkage.) Specific examples of the group CPH2P+I- include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl 'n-hexyl, n-heptyl, n-octyl , n-decyl, n-decyl 'n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl 'n-hexadecyl, n-heptadecyl, n-octadecyl , n-nonadecyl, n-icosyl, etc. The two amine groups of the diaminophenyl group are preferably 2,4-position or 3,5-position relative to other groups. Specific examples of the compound represented by -1 ) include, for example, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, and pentadecyloxy group- 2,4-Diaminobenzene,hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-di Aminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, Octadecyl-2,5-diamino benzene, and the following formula (D-1-i) ~ (d-1-3) compounds represented respectively.

〇5^ (D-1-2) C5H11 (D-1-1)

-27- 201206978 In the above formula (D-1), m and η are 0 when they are not different from each other. These diamines can be used individually or in combination of 2 or more types. The tetracarboxylic dianhydride used in the synthesis reaction of polylysine and the use ratio thereof are preferably 0.2 to 2 equivalents, more preferably 0.3, based on the acid anhydride group of the amino dianhydride contained in 1 equivalent of the diamine compound. The proportion of the amount. The synthesis reaction of poly-proline is preferably carried out in an organic solvent, preferably: 〜150 ° C, more preferably at a temperature of 〇 ° C to 100 ° C, preferably carried out in an hour, preferably 2 ~ 1 0 hours. Among them, the organic solvent is not particularly limited as long as it dissolves the synthesized polyamic acid, and for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, hydrazine, hydrazine Aprotic polar solvents such as guanamine, hydrazine, hydrazine-dimethylimidazolidinone, dimethyl hydrazine, γ-butyltetramethylurea, hexamethylphosphonium triamine; m-cresol, xylenol, The amount of the phenol-soluble organic solvent such as phenol or halogenated phenol (a) is the total amount of the tetraacid dianhydride and the diamine compound to the reaction solution (a + b) is preferably 0.1 to 50% by weight, 5 to 3 An amount of 0% by weight. As above, the reaction solution solution formed by dissolving polylysine can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent and a separated polyamine after the polyamine acid contained in the solution. After acid purification, it is used to prepare a liquid crystal alignment agent. When the polyglycine is dehydrated and closed to form a polyimine, the solution can be directly used for the dehydration ring closure reaction; or the reaction of the diamine can be separated, the tetraacid is 1.2 to 1.2 when £2 0 °C 0 · 5~24 Examples thereof include dimethyl lactones and the like.匮(b) is better. The reverse reaction may be carried out by using the poly-proline in some of the above-mentioned reverse liquids for dehydration ring closure reaction or by purifying the separated polyamine acid for use in a dehydration ring closure reaction. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or by vacuum-reducing the organic solvent in the reaction solution by an evaporator or the like. . In addition, 'the method of dissolving the polylysine into an organic solvent and then precipitating in a poor solvent; or by repeating one or more times to dissolve the polylysine into an organic solvent, the strip is washed. After the solution, the polyamine acid is purified by a method such as distillation under reduced pressure using an evaporator. {Polyimide] The above polyimine can be synthesized by dehydrating a hydrazine ring structure of a polyaminic acid obtained as described above. At this time, the yttrium acid structure can be completely dehydrated and closed, and the ruthenium can be completely imidized; or a part of the structure of the tyrosine acid can be dehydrated and closed to form a part of the guanidine structure and the quinone ring structure. Imine. The polyamidene used in the present invention preferably has a ruthenium iodide ratio of 40% or more, more preferably 50 to 95%. The dehydration ring closure of poly-proline can be carried out by (i) heating the poly-proline, or by (ii) dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. It needs to be carried out by heating. The reaction temperature in the method of heating poly-proline in the above (i) is preferably 5 Torr to 2 Torr °C, more preferably 6 Torr to 17 °C. When the reaction temperature is less than 5 Torr, the dehydration ring closure reaction cannot be sufficiently carried out; if the reaction temperature exceeds 200 ° C, the molecular weight of the polyamidene obtained from -29 to 201206978 may be lowered. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably from 1 to 20 mol per mol of the structural unit of 1 mol of the polyaminic acid. The dehydration ring-closure catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. However, it is not limited to this. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol with respect to the dehydrating agent used for 1 m Torr. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 18 (TC, more preferably from 10 to 150 ° C. The reaction time is preferably from 5 to 20 hours, more preferably from 1 to 8 hours. The above method (i) The polyimine obtained in the present invention can be directly used for preparing a liquid crystal alignment agent, or after the obtained polyimine is refined, and used for preparing a liquid crystal alignment agent. On the other hand, in the above method (ii), a reaction solution containing polyiminoimine. The reaction solution can be directly used for preparing a liquid crystal alignment agent, and can also be used to prepare a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; After the amine, it is used to prepare a liquid crystal alignment agent; or after the separated polyimine is refined, it is used to prepare a liquid crystal alignment agent. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement is suitably used. The separation and purification of the imine can be carried out by the same operation as described above for the separation and purification method of polylysine. -30- 201206978 {Use ratio of other polymers) The present invention When the liquid crystal alignment agent contains the above specific polymer and other polymers, the ratio of use as the other polymer is preferably the same as the total amount of the polymer (refer to the total amount of the specific polymer and other polymers, the same applies hereinafter). It is 99% by weight or less, more preferably 95% by weight or less, still more preferably 80% by weight or less, and particularly preferably 50% by weight or less. By such a use ratio, the effect of the present invention can be impaired, and the electrical properties of the formed liquid crystal alignment film can be further improved. Further, it is preferable to contribute to the reduction of the cost of the liquid crystal alignment agent. [Epoxy compound] The epoxy compound may be contained in the liquid crystal alignment agent of the present invention from the viewpoint of further improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromopentyl glycol diglycidyl ether, tetraglycidyl-2,4-hexyl Glycol, :^,:^,:^',:^-tetraglycidyl-m-xylylenediamine, I,3-di(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl, yl-4,4,diaminodiphenylmethane, anthracene, hydrazine diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl - Aminomethylcyclohexane or the like is preferred. In the case where the liquid crystal alignment agent of the present invention contains an epoxy compound, the content thereof is preferably 100 parts by weight or less, more preferably 30 parts by weight or less, based on the total amount of the polymer. [Functional decane compound] The above functional decane compound can be used for the purpose of improving the adhesion between the obtained liquid crystal alignment film and the substrate. Examples of the functional sand compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropylamine. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxy decane, 3- guanidinopropyl trimethoxy decane, 3- guanidinopropyl triethoxy decane, Ν ethoxycarbonyl-3-aminopropyl trimethoxy decane, Ν-ethoxy Carbonylaminopropyl triethoxy sand pot, Ν-triethoxy oxalate propyl triethylene triamine, Ν-trimethoxymethyl propyl propyl triethylene triamine, 1 〇 _ tri Oxymethane alkyl-1,4,7-triazadecane, 10-triethoxymethylidene-anthracene, 4,7-triazadecane, 9-trimethoxycarbamido-3, 6-diazaindolyl acetate, 9-diethoxyformamidin-3,6-diazaindolyl acetate, Ν-benzyl-3-aminopropyltrimethoxydecane, Ν_Benzyl-3-aminopropyltriethoxy oxime, Ν-phenyl-3·aminopropyltrimethoxysilane, Ν-phenyl-3·aminopropyl An ethoxylated sand, Ν-(oxyethyl)-3-aminopropyltrimethoxy sulphate, fluorene-bis(oxyvinyl)-3-aminopropyltriethoxy decane, 3_ glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc., and further, as disclosed in Patent Document 8 (Japanese Patent Laid-Open No. 32- A reaction product of tetracarboxylic dianhydride and a decane compound having an amine group described in 201206978 63-291922. When the liquid crystal alignment agent of the present invention contains a functional decane compound, the content thereof is preferably 1 part by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the total of the polymer. <Liquid crystal alignment agent> As described above, the liquid crystal alignment agent of the present invention contains a specific polymer as an essential component, and may contain other components as needed, and it is preferred to dissolve each component in an organic solvent to prepare a solution. combination. As the organic solvent which can be used for preparing the liquid crystal alignment agent of the present invention, it is preferred to dissolve the specific polymer and other components which are optionally used without reacting with them. The organic solvent may, for example, be N-methyl-2-indolepyridone, γ-butyrolactone, γ-butylide, N,N-dimethylformamide, N,N- Dimethylacetamide '4·hydroxy-4_methyl-2-pentanone, ethylene glycol monomethyl acid, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxypropionic acid Ethyl ester, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl Acid, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethyl ether-ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, one ethylene Alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl hydrazine, isoamyl propionate 'isoamyl butyrate, diisoamyl ether, ethylene carbonate As the vinegar, propylene carbonate or the like, it is preferred to use one or more selected from them. -33-201206978 A preferred solvent for preparing the liquid crystal alignment agent of the present invention is a solvent obtained by combining one or two or more kinds of the above organic solvents, and is contained in a liquid crystal alignment agent at a preferred solid concentration concentration described below. The components do not precipitate 'and the surface tension of the liquid crystal alignment agent is in the range of 25 to 40 mN/m. When the substrate to which the liquid crystal alignment agent of the present invention is applied has high solubility in the above organic solvent (for example, when a flexible substrate such as triethyl cellulose (TAC) is used), the substrate may not be dissolved or the substrate may be difficult to dissolve. The other organic solvent is used together with or in place of the above organic solvent. Examples of such other organic solvents include cyclohexane, cyclopentanone, cyclohexanone, ethanol, isopropanol, n-propanol, isobutyl, n-butanol, propylene glycol methyl ether, ethyl acetate, and acetic acid. Propyl ester, isopropyl acetate, butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellulose Agent, propylene glycol monomethyl ether, ethyl cellosolve, 2,3-pentanedione, i,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethyl Ethoxyethane or the like; one or more selected from them may be used. The ratio of use of the above-mentioned organic solvent to other organic solvents can be appropriately determined after investigating the solubility of each component contained in the liquid crystal alignment agent of the present invention and the solubility of a suitable substrate. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the weight of all the components other than the solvent in the liquid crystal alignment agent, is a ratio of the total weight of the liquid crystal alignment agent, and is preferably 1 to 10 by weight in consideration of viscosity, volatility, and the like. The range of %. The liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film formed of a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight to -34 to 201206978, the film thickness of the coating film is too small, and it may be difficult to obtain a good liquid crystal. Orientation film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and a satisfactory liquid crystal alignment film may not be obtained, or the viscosity of the liquid crystal alignment agent may increase, and the coating property may be insufficient. The range of the solid content concentration is particularly preferably in the range of 1.5 to 6% by weight, when the spin coating method is used. When the printing method is used, the concentration of the solid content is particularly preferably in the range of 3 to 9 % by weight, whereby the solution viscosity is in the range of 1 2 to 50 mPa·s. When the ink jet method is used, the concentration of the solid content is particularly preferably 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 〇 ° C to 200 ° C, more preferably 0 ° C to 40 ° C. <Method of Forming Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention is suitably used for forming a liquid crystal alignment film by a photo-alignment method. When the liquid crystal alignment agent of the present invention is used for a TN type, an STN type or a horizontal electric field type liquid crystal display element, particularly when used for a horizontal electric field type liquid crystal display element, or when used for manufacturing a retardation film, the liquid crystal alignment agent can be maximized. The effect of the invention is therefore preferred. When the liquid crystal alignment film is formed using the liquid crystal alignment agent of the present invention, it can be carried out by a method of the following steps: (a) a step of applying a liquid crystal alignment agent of the present invention on a substrate to form a coating film of a polymer; and (b) The coating film of the above polymer is irradiated with radiation to form a liquid crystal alignment film. -35- 201206978 Hereinafter, the above steps (a) and (b) will be described. (a) applying a liquid crystal alignment agent of the present invention to a substrate, wherein, in the case where the liquid crystal alignment agent of the present invention is used for a liquid crystal display element, a pair of through-substrate provided with a pattern is formed, each of which is formed The transparent conductive film forms a clear liquid crystal alignment agent to form a coating film. In the liquid transverse electric field type liquid crystal display device of the present invention, a pair of opposite substrates of the substrate of the transparent conductive film or the electrode of the metal film pattern on one surface is formed, and the surface of the comb-shaped electrode is coated on each side. In the above two cases, the liquid crystal alignment agent of the invention may be a glass such as glass or soda glass, or a transparent substrate such as polybutylene terephthalate, polyether oxime or polycarbonate. Wait. The ITO film formed of the transparent conductive film Έ In203-Sn02, a film formed of Sn02, or the like. As the above metal film, for example, a film can be used. In order to form a pattern of a transparent conductive film and a metal film, a transparent conductive film is formed, and a photolithography method or a method is used. When a transparent conductive film is formed, a method using a mask or the like is obtained. When the liquid crystal alignment film of the liquid crystal alignment agent is coated on the transparent substrate, the two sides of the coating film TN type or the STN type bright conductive film are coated on the transparent substrate, and the present crystal alignment agent is applied to have a comb-like shape. A coating film is formed on the surface of the electrode and the opposite substrate. For example, a crucible formed of a metal such as floatate formic acid, polystyrene, or the like is used to form a retardation film which is formed of a metal such as NESA (registered trademark) chrome, for example, by a sputtering method or the like. The liquid crystal of the present invention is formulated to form a coating film. Examples of the transparent substrate used in this case include glass substrates such as float glass and soda glass; triethylenesulfonyl cellulose (TAC), polyethylene terephthalate, and polybutylene terephthalate. Diester, polyether oxime, polyamidamine, polyimine, polymethyl methacrylate, polycarbonate, and the like. Among them, 'TAC' is a material used as a protective layer of a polarizing film which plays an important role in a liquid crystal display element. In any of the above cases, when a liquid crystal alignment agent is applied onto a substrate, in order to improve the adhesion between the substrate or the transparent conductive film and the electrode and the coating film, a functional decane compound may be applied to the substrate and the electrode in advance. Titanate compounds and the like. The coating of the liquid crystal alignment agent onto the substrate is preferably carried out by an appropriate coating method such as an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method, and then the coated surface is preheated (prebaked) and then fired (after Baking) to form a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes. Carry out 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to Ιμηι, more preferably 〇.〇〇5 to 0.5 μιη. (b) Step of irradiating radiation to the coating film of the polymer The coating film formed in the above step (a) is irradiated with linearly polarized light or partially polarized radiation or unpolarized radiation to impart liquid crystal alignment energy. Here, as the radiation, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, and ultraviolet rays having a wavelength of more than 300 nm and having a wavelength of 4 〇 Onm or less are preferably contained. In this case, in order to prevent the influence of the molecular chain or the like of the polymer from being cut off by the short-wavelength -37-201206978 ultraviolet irradiation with high energy, the coating film is deteriorated. It is preferable to filter the UV filter having an ultraviolet ray having a wavelength of 300 nm or less. Irradiation is performed. When the irradiated radiation is linearly polarized or partially polarized, it may be irradiated from the direction of the vertical substrate surface or may be irradiated from the oblique direction, or may be irradiated in combination. When irradiating non-polarized radiation, the direction of illumination must be the direction of tilt. As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium 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 preferred wavelength region can be obtained by a mechanism for using the light source together with, for example, a filter, a diffraction grating, or the like. The irradiation amount of the radiation is preferably from 100 to 50,000 J/m 2 , more preferably from 300 to 20,000 J/m 2 °. Here, when the liquid crystal alignment film is used for producing a retardation film, it can be conveniently formed in the plane of the liquid crystal alignment film. Multiple areas with different alignment states. Thus, the produced retardation film has a plurality of regions having different polarization states, and is suitable as, for example, a retardation film for 3D image display. In order to form such a liquid crystal alignment film having a plurality of regions having different alignment states, for example, the following methods can be mentioned. When the coating film is irradiated with radiation to form a liquid crystal alignment film, when the radiation to be irradiated is linearly polarized or partially polarized, the direction in which the direction in which the polarization of the irradiation radiation is projected onto the coating film surface is different in each region; In the case where the irradiated radiation is non-polarized, it can be carried out by changing the irradiation direction of each region. In any of the above cases -38 - 201206978, the degree of change in the direction of the adjacent regions is preferably 70 to 110 °', more preferably 85 to 95. The best is 90. . Such irradiation of changing the polarization direction or the irradiation direction for each region of the coating film may be performed by, for example, blocking a part of the coating film by the first irradiation with radiation having the first polarization direction or the irradiation direction, and this time the first irradiation After the exposure portion is shielded from light, the region where only the first illumination is shielded is performed by the second irradiation by the radiation having the second polarization direction or the irradiation direction. The shading can be performed, for example, by a mask having a desired opening pattern. When the retardation film produced by the method of the present invention is used for a retardation film for 3D image display, it is possible to easily form a state in which two regions having different striped alignment states are distributed on the liquid crystal alignment film surface. The liquid crystal alignment film can be formed as above. The liquid crystal alignment film is suitable for use in the production of a liquid crystal display or a retardation film. Hereinafter, a method of producing a liquid crystal alignment element and a method of producing a retardation film will be sequentially described. <Manufacturing Method of Liquid Crystal Display Element> A liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced, for example, as follows. First, as in the above steps (a) and (b), a pair of substrates on which a liquid crystal alignment film is formed are prepared, and liquid crystal is sandwiched between the pair of substrates to fabricate a liquid crystal cell having such a structure. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a currently known method. First, in order to arrange the liquid crystal alignment films in the opposite direction, the two substrates are arranged to face each other through a gap (box gap), and the peripheral portions of the two substrates are bonded together using a sealant, and the surface of the substrate is -39-201206978. The liquid crystal cell can be manufactured by injecting a liquid crystal into the cell gap of the sealant and sealing the injection hole. The second method is a method called ODF (Drip Injection). A predetermined position on one of the two substrates forming the liquid crystal alignment film is coated with, for example, a UV curable sealing material, and then liquid crystal is dropped on the liquid crystal alignment film surface, and the other substrate is bonded and the liquid crystal is aligned. The film is opposed, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, and a liquid crystal cell can be manufactured. In the case of any of the methods, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal used is isotropic, and then slowly cool to room temperature to remove the flow alignment at the time of liquid crystal charging. Then, by attaching a polarizing plate to the outer surface of the liquid crystal cell, the liquid crystal display element of the present invention can be obtained. Here, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the irradiation linearly polarized radiation in the two substrates forming the liquid crystal alignment film and the angle between each substrate and the polarizing plate. As the sealant, for example, an epoxy resin containing an alumina sphere as a separator and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal, a dish liquid crystal or the like can be used. For example, a liquid crystal having a positive dielectric anisotropy of a nematic liquid crystal can be used. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal 'triphenyl liquid crystal, or biphenyl cyclohexane can be used. Liquid crystal, pyridine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, -40-201206978 "Cholesteric liquid crystal such as cholestyl chloride, cholesterol phthalate, cholesterol carbonate or the like may be further added to the above liquid crystal; under the trade names "C-15", "CB- 15" (the above-mentioned chiral reagent sold by Merck); a ferroelectric liquid crystal such as methoxybenzylidene-p-amino-2-methylbutylcinnamate or the like. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate formed by stretching a polyvinyl alcohol while being aligned, and sandwiching a polarizing film called absorbing iodine called "H film" with a cellulose acetate protective film or by the ruthenium film itself. A polarizing plate is formed. <Method for Producing Phase Difference Film> The phase difference film of the present invention can be produced, for example, as follows. First, as in the above steps (a) and (b), a substrate on which a liquid crystal alignment film is formed is prepared, and a retardation film can be obtained by a process including the following steps: (Ο Coating polymerization on a liquid crystal alignment film) The step of forming a coating film of a polymerizable liquid crystal, and (d) performing one or more processes selected from the group consisting of heating and irradiating radiation to perform a step of curing the coating film of the polymerizable liquid crystal. Steps (c) and (d) are explained. (c) Step of applying a polymerizable liquid crystal to form a coating film of a polymerizable liquid crystal on the coating film of the polymer after the irradiation of the radiation - 41 - 201206978 In this step, The liquid crystal alignment film is coated with a polymerizable liquid crystal. The polymerizable property used herein is limited by a liquid crystal compound which is heated or irradiated with radiation. For example, Non-Patent Document 2 ("UV Application", Liquid Crystal, Vol. 3, No. 1) can be used. In the case of the liquid crystal compound of the nematic type, the polymerizable liquid crystal may be used alone or in combination, and may be selected from photopolymerization initiators. A liquid crystal having no polymerizable property (for example, a twisted nematic crystal, a discotic liquid crystal, or the like), a chiral reagent, a solvent, or the like is used together. As a method of applying the polymerizable liquid crystal, a spin coating method, a printing method, or the like may be employed. A suitable method such as an inkjet method. The thickness of the coating film of the polymerizable liquid crystal can be a film thickness of an optical property which is desirable. For example, when a wavelength of 1 / 2 wavelength plate is produced, a phase difference of 24 〇 is formed. The film thickness of 300 nm is a film thickness of 12 0 to 15 Onm in the case of a quarter wave plate, and the optical properties of the most polymerizable liquid crystal having a target phase difference are obtained. For example, in a polymerizable liquid crystal (RMS03-013C) When the film thickness used is suitably in the range of 〇.6 to 1.5 μm, the appropriate film thickness for polymerization can be easily determined by those skilled in the art by at least a part of the liquid crystal as long as it is possible. The special hardenable liquid crystal and the mixture of two or more types described in ρρ34 to 42) are used to obtain a visible light of 540 nm by using a thermal polymerization initiator, a liquid crystal, a cholesterol liquid or more, and a polymerization property by, for example, a roll coating method. The phase difference of the film is such that the phase difference is selected to be a good film thickness. According to the use of a coating film using a half-wave plate liquid crystal manufactured by Merck Co., Ltd., a preparation test is selected - 42 - 201206978 (d), which is selected from the group consisting of heating and irradiation of radiation. In the step of curing the coating film of the polymerizable liquid crystal by heating, the heating condition at the time of curing the polymerizable liquid crystal varies depending on the polymerizability of the polymerizable liquid crystal to be used. For example, Merck is used. In the case of the produced polymerizable liquid crystal (RMS03-013C), it is preferably a heating temperature in the range of 40 to 8 ° C and a heating time of 20 seconds to 10 minutes. When the polymerizable liquid crystal is cured by irradiation with radiation, it is used. Examples of the radiation include non-polarized ultraviolet rays and the like. The amount of radiation to be irradiated is preferably 1, 〇〇〇J/m2 or more and less than 100,000 J/m2, more preferably 10,000 to 5,000 J/m2 ° as described above. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by these examples. The weight average molecular weight (Mw) in the synthesis example of the following polymer is a polystyrene-converted oxime measured by gel permeation chromatography under the following conditions.

Column: Tosoh (manufactured by Tosoh), TSKgel GRCXLII Solvent: tetrahydrofuran Temperature: 40 ° C Pressure: 68 kgf / cm 2 or less The "inactive atmosphere" described in the synthesis example is a nitrogen atmosphere. Further, in the following synthesis examples, each compound ' is repeatedly synthesized as needed by the following synthesis route to secure the amount necessary for the subsequent synthesis example of the polymer. -43-201206978 <Synthesis of Dicarboxylic Acid> In the following Synthesis Examples DC-1 to DC-4, compounds represented by the above formulas (DC-1) to (DC-4) are synthesized (hereinafter, respectively As "compound (DC - 1)", "compound (DC - 2 )", "compound (d C - 3 )" and "compound (DC-4)"), as a dicarboxylic acid having the structure (1) . Synthesis Example DC-1 (1) Synthesis of 4-propenyloxybenzoic acid 13.8 g (10 mmol) of 4-hydroxybenzoic acid, 8 g (200 mmol) of sodium hydroxide and 4 mL of pure water were added. The 1 L three-necked flask of the dropping funnel was cooled in an ice bath. Thereto, 20 mL of a dichloromethane solution containing 10.86 g (120 mmol) of acrylonitrile chloride was added dropwise from the dropping funnel over 1.5 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours in an ice bath, and after the temperature of the reaction mixture was returned to room temperature, the mixture was stirred for 3 hours to carry out a reaction. Next, after the reaction mixture was again subjected to an ice bath, 1 equivalent of hydrochloric acid was added dropwise to make the liquid property of the reaction mixture acidic. The precipitated solid was collected using a suction funnel and recrystallized from ethanol to obtain 16 g of 4-propenyloxybenzoic acid. (2) Synthesis of Compound (DC-1) This synthesis was carried out in an inert atmosphere. 5 g of 4-propenyloxybenzoic acid obtained above, 5.3 g of 4-bromobenzoic acid, 60 mg of palladium acetate, ruthenium.32 g of tris(o-tolyl)phosphine llg of triethylamine and 4 〇mL of dimethyl The hydrazine was mixed in a 200 mL flask and stirred at 14 ° C for 6 hours to carry out a reaction. After the temperature of the reaction mixture was returned to room temperature, 200 mL of 1 equivalent of hydrochloric acid was added. The precipitated solid was filtered and recrystallized from ethanol to give 6 g of compound (D C -1). -44- 201206978 Synthesis Example DC - 2 o) - Synthesis of (4 _ propylene oxyphenyl) A hospital in a 200 mL three-necked flask with a dropping funnel, 10 g of 4-hydroxydiphenylmethane 'llg Triethylamine and 6 〇 mL of tetrahydrofuran form a solution. After the solution was ice-cooled, 5 mL of a tetrahydrofuran solution containing 10 g of propylene chloride was added dropwise from the dropping funnel. After completion of the dropwise addition, the reaction mixture was further stirred for 3 hours in an ice bath, and the reaction mixture was washed with a mixed solvent of ethyl acetate and water. The organic layer was recovered, dried over magnesium sulfate, and then evaporated to give an organic solvent to give 15 g of bis(4-propenyloxyphenyl)methane (2) Compound (DC-2). The synthesis was carried out in an inert atmosphere. 8 g of the above-obtained bis(4-propenyloxyphenyl)methane, l〇.5 g of 4-bromobenzoic acid, uomg of palladium acetate, 〇.63 g of tris(o-tolyl)phosphine, 21 g of triethyl The amine and 90 mL of dimethylacetamide were mixed in a 300 mL flask and stirred at 140 ° C for 6 hours to carry out a reaction. After the temperature of the reaction mixture was returned to room temperature, 500 mL of 1 equivalent of hydrochloric acid was added. The precipitated solid was filtered and recrystallized from ethanol to give 4 g of compound (DC-2). Synthesis Example D C - 3 (1) Synthesis of 1,4-dipropenyloxybenzene Into a 300 mL three-necked flask equipped with a dropping funnel, 10 g of hydroquinone, 20 g of triethylamine and 0 mL of tetrahydrofuran were placed to form a solution. After the solution was ice-cooled, 9OmL of a tetrahydrofuran solution containing 19 g of acrylonitrile chloride was added dropwise thereto. After further stirring for 3 hours in an ice bath, the obtained reaction -45 - 201206978 mixture was washed with a mixed solvent of ethyl acetate and water. The organic layer was recovered, dried over magnesium sulfate, and the organic solvent was distilled off to give 6 g of 1,4-dipropenyloxybenzene. (2) Synthesis of Compound (D C - 3 ) The synthesis was carried out in an inert atmosphere. 8 g of the 1,4-dipropenyloxybenzene obtained above, 15 g of 4-bromobenzoic acid, 165 mg of palladium acetate, 0.9 g of tris(o-tolyl)phosphine, 30 g of triethylamine and 130 mL of dimethyl The guanamine was mixed in a 500 mL flask and stirred at 140 ° C for 6 hours to carry out a reaction. After completion of the reaction, after the temperature of the reaction mixture was returned to room temperature, 7 mL of 1 equivalent of hydrochloric acid was added. The precipitated solid was filtered and recrystallized from ethanol to give 8 g of compound (DC-3). Synthesis Example DC-4 In the same manner as in Synthesis Example DC-2 except that 11.4 g of 2-fluoro-4-bromobenzoic acid was used instead of 4-bromobenzoic acid in the above-mentioned Synthesis Example DC-2. g compound (DC-4). <Polymerization Example of Specific Polymer> Synthesis Example SP-1 In a 50 mL flask, 3 g (0.01 mol) of the above-mentioned Synthesis Example DC-1 as a polyfunctional carboxylic acid was introduced to obtain a compound (DC-1), 0.83 g. (0.01 mol) as a compound represented by the above formula (DE-1) which is a polyfunctional epoxy compound and 1 g of N-methyl-2-pyrrolidone as a solvent, which was stirred at 140 ° C The reaction was carried out for 6 hours to obtain a solution containing the polymer (SP-1) as a specific polymer. The weight average molecular weight (Mw) of the polymer (SP-1) contained in the solution is 4,200 〇-46 - 201206978 Synthesis Examples SP-2 to SP-20 and Synthesis Example rp_i except in the above Synthesis Example SP·1, The polyfunctional carboxylic acid and the polyfunctional epoxy compound were used in the same manner as in the above-described examples and in the same manner as in the synthesis example SP-1, except that the polyfunctional carboxylic acid and the polyfunctional epoxy compound were used. -2) A solution of ~(SP-20) and a polymer (rp-1) as another polymer. Further, in Synthesis Examples SP-9 and SP-19, two compounds were used as a mixture of polyfunctional epoxides, and in Synthesis Example SP-2, two compounds were used as a mixture of polyfunctional phthalic acids. The synthesis example rp_l is a comparative synthesis example. The molecular weight of the polymer contained in each solution is shown in Table 1. The abbreviations of the polyfunctional carboxylic acid and the polyfunctional epoxy compound in Table 1 are respectively the following meanings. [$functional carboxylic acid] DC-1 : Compound (DC-1) obtained by the above Synthesis Example DC-1 DC-2: Compound (DC-2) obtained by the above Synthesis Example DC-2: DC-3: Synthesis Example DC -3 obtained compound (DC-3) DC-4: Compound (DC-4) obtained by the above Synthesis Example DC-4 tc-Ι: pyromellitic dianhydride α: a compound represented by the following formula (α)

-47- 201206978 [Polyfunctional epoxy compound] DE-1 : Compound DE-2 represented by the above formula (DE-1): Compound DE-3 represented by the above formula (DE-2): the above formula (DE- 3) The compound DE-4 shown: the compound DE-5 represented by the above formula (DE-4): the compound DE-6 represented by the above formula (DE-5): represented by the above formula (DE-6) Compound DE-7: a compound represented by the above formula (DE-7): DE-8: a compound represented by the above formula (DE-8): Ν, Ν, Ν, 'Ν, tetraglycidyl-inter Dimethylphenyl diamine Table 1 Synthesis Example Polyfunctional carboxylic acid polyfunctional epoxy compound Polymer type (mmol) Species (mmol) Name Mw SP-1 DC-1 10 DE-1 10 SP-1 4,200 SP-2 DC-1 10 DE-2 10 SP-2 11,000 SP-3 DC-1 10 DE-3 10 SP-3 12,000 SP-4 DC-1 10 DE-4 10 SP-4 12,500 SP-5 DC-1 10 DE -5 10 SP-5 7,700 SP-6 DC-1 10 DE-6 10 SP-6 9,600 SP-7 DC-1 10 DE-7 10 SP-7 13,000 SP-8 DC-1 10 DE-8 10 SP- 8 12,800 SP-9 DC-1 DE-3 5 SP-9 7,800 1U DE-6 5 SP-10 DC-2 10 DE-3 10 SP-10 3,800 SP-11 DC-2 10 DE-5 10 SP-11 3,300 SP-12 DC-2 10 DE-6 10 SP-12 4,100 SP-13 DC-3 10 DE-3 10 SP-13 6,600 S P-14 DC-3 10 DE-5 10 SP-14 5,100 SP-15 DC-3 10 DE-6 10 SP-15 4,500 SP-16 DC-4 10 DE-3 10 SP-16 4,400 SP-17 DC- 4 10 DE-5 10 SP-17 3,700 SP-18 DC-4 10 DE-6 10 SP-18 4,000 SP-19 DC-4 DE-6 9.5 SP-19 7,800 ιυ te-1 0.25 SP-20 DC-4 9.5 DE-6 SP-20 7,100 tc-1 0.25 10 rp-1 α 10 DE-3 10 rp-1 8,700 -48- 201206978 <Synthesis of Other Polymers> [Synthesis of Polylysine] Synthesis Example PA - 1 2008(1.011101) 1,2,3,4-cyclobutyric acid-hepatic acid as tetracarboxylic dianhydride and 210 g (l.〇mol) of 2,2,-dimethyl- 4 as diamine 4'_. Diaminobiphenyl 'dissolved in 3,670 g of N-methyl-2-pyrrolidone' was reacted at 40 ° C for 3 hours to obtain 10% by weight of polyaminic acid (PA-1). )The solution. The solution had a solution viscosity of 160 mPa_s. Synthesis Example PA-2 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexane bis(methylamine) were dissolved to 3 29.3 g of N In the methyl-2-pyrrolidone, the reaction was carried out at 60 ° C for 6 hours to obtain a solution containing polyglycine (PA-2). The solution containing poly-proline (PA-2) is converted into polyacetamide in an amount equivalent to 17.5 g for synthesizing the polyimine (P 1-1) described below, and the remaining portion is used for A liquid crystal alignment agent is prepared. [Synthesis of Polyimine] Synthesis Example PI-1 The polyamic acid in the polylysine (PA-2) obtained in the above Synthesis Example PA-2 was selected, which corresponds to an amount of 17.5 g, and was added thereto. 23 2.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride, stirred at 120 ° C for 4 hours, dehydrated and converted to ruthenium iodide to obtain polyimine (PI_ 1) solution. The ruthenium imidization ratio of the polyimine (PI-1) contained in the solution was 60%. -49-201206978 Example 1 <Preparation of Liquid Crystal Aligning Agent> In a solution containing the polymer (SP-1) obtained in the above Synthesis Example SP-1 as a specific polymer, N-methyl-2 was added thereto. The pyrrolidone and butyl cellosolve 'formed a solvent composition of N.methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio), and a solid concentration of 3.0% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. <Evaluation of Liquid Crystal Alignment> (1) Production of Liquid Crystal Display Element The liquid crystal alignment agent prepared above was applied onto the transparent electrode surface of a glass substrate having a transparent electrode formed of a ruthenium film by a spin coater. After prebaking for 1 minute on a hot plate at 80 °C, it was heated at '200 °C' for 1 hour (post-baking) in an oven which had been replaced with nitrogen in the tank to form a coating film having a film thickness of 0.1 μηα. Then, on the surface of the coating film, using a Hg-Xe lamp and a Glan-Taylor prism, a bright wire having a wavelength of 3 1 3 nm was irradiated from a direction perpendicular to the substrate, and a glow wire of 3 0 Onm or less was cut using a UV filter. The polarized ultraviolet light is 10,000 J/m 2 to form a liquid crystal alignment film. The same operation was repeated to manufacture a pair of (two pieces) substrates having a liquid crystal alignment film. On the outer periphery of the surface of the substrate having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 3 · 5 μm is applied by screen printing, and the liquid crystal alignment film surface of the pair of substrates is applied. In the opposite direction, the bonding was performed so that the projection direction of the ultraviolet light axis of each substrate toward the substrate surface was reversed, and the adhesive was thermally cured at 1 5 ° C for 1 hour. Next, from the liquid crystal injection -50-201206978, the liquid crystal injection port was sealed by an epoxy-based adhesive after filling the liquid crystal "MLC-7028" manufactured by Merck in the gap between the two substrates. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Next, the polarizing plates are bonded to the outer surfaces of the two substrates such that the polarization directions thereof are orthogonal to each other, and the direction of the irradiation of the ultraviolet ray of the liquid crystal alignment film on the substrate surface is 45. From the perspective of manufacturing liquid crystal display elements. (2) Evaluation of liquid crystal alignment property The liquid crystal alignment element of the liquid crystal display device produced by the above-mentioned liquid crystal display device was observed by an optical microscope, and when the abnormality region was not observed, when the liquid crystal alignment property was "good", the liquid crystal alignment of the liquid crystal display device was observed. <Evaluation of burn-in property> (1) Production of a horizontal electric field type liquid crystal display element In addition to the above (1) evaluation of liquid crystal alignment property, (1) production of liquid crystal display element, The glass substrate uses a glass substrate having a comb-like conductive film pattern formed of chromium having two systems and a glass substrate having no conductive film as a pair, respectively on the conductive film of the substrate having the comb-shaped conductive film and the other substrate In the same manner as in the production of (1) liquid crystal display element (1) liquid crystal display element, the liquid crystal display element is coated on one surface, and the structure of the electrode pattern on the glass substrate is used. The simplified diagram is shown in Fig. 1. The conductive film pattern of the two systems of the horizontal electric field type liquid crystal display element manufactured above is It is referred to as "electrode A" and "electrode B" respectively. -5 1- 201206978 (2) Evaluation of burn-in properties The horizontal electric field type liquid crystal display element manufactured above was placed in an environment of 25 ° C '1 atm, not at the electrode. A voltage applied to B was applied to electrode A for a combined voltage of 3.5 V AC and 5 V DC for 2 hours. Then, a voltage of 4 V was applied to both electrode A and electrode B. The measurement was started from the two electrodes. When the voltage of 4 V is exchanged, the time when there is no difference in the light transmittance between the electrode A and the electrode B is visually confirmed. When the time is less than 20 seconds, the burn-in property is evaluated as "optimal"; in 20 seconds or more, less than 60 In the second case, the burn-in property was evaluated as "excellent"; when it was 60 seconds or more and less than 100 seconds, the burn-in property was evaluated as "good"; when it was more than 100 seconds, less than 150 seconds, it would burn. The screen property was evaluated as "尙可"; then, at more than 150 seconds, the burn-in property was evaluated as "not good". In this case, the burn-in property of the horizontal electric field type liquid crystal display element was "good". ''. Examples 2 to 18, 2 5 and 2 6 and Comparative Example 1 In the same manner as in Example 1, except that a solution containing the polymer and the amount of the polymer described in Table 2 was used as the polymer in the above Example 1 A liquid crystal alignment agent was prepared and manufactured to evaluate and evaluate the liquid crystal display element. The evaluation results are shown in Table 2. Further, in Comparative Example 1, other polymers were used instead of the specific polymer. -52- 201206978 Example 1 9 In this example, a specific polymer and other polymers were used in combination. Only the solution containing polylysine (pa 丨 得到) obtained by the above Synthesis Example PA-1 was converted into an amount of 80 parts by weight of polylysine (PA-1) contained therein, and 20 parts by weight was added thereto. Part of the specific polymer (SP-10) obtained in the above Synthesis Example SP-10, and then adding N-methyl-2-pyrrolidone and butyl cellosolve' to form a solvent composition of N-methyl-2-pyrrolidone A solution of butyl cellosolve = 50:50 (weight ratio) and a solid content concentration of 3% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. Then, using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 2. Example 20 to 24 A liquid crystal display element was produced and produced in the same manner as in Example 19 except that a solution containing a polymer and a polymer of the type and amount described in Table 2 was used as the specific polymer and the other polymer, respectively. Evaluation. Further, the specific polymer and other polymers form a solution containing the polymer of the kind described in Table 2 for the preparation of a liquid crystal alignment agent. For the specific polymer and other polymers, the amounts described in Table 2 are the amounts of the polymer contained in the polymer solution used, respectively. In Examples 2 and 24, two other polymers were used, respectively. The evaluation results are shown in Table 2. -53- 201206978 Table 2 Polyester content of liquid crystal alignment agent fine liquid crystal display element specific polymer Other polymer liquid crystal burn-in type (parts by weight) Type (parts by weight) Orientation__Μ - Example 1 SP-1 100 0 Good example 2 SP-2 100 0 Good humiliation _ Example 3 SP-3 . 100 0 Good Excellent Example 4 SP-4 100 0 Excellent and excellent - Example 5 SP-5 100 • 0 Good and excellent one implementation Example SP-6 100 • 0 Good Good Example 7 SP-7 100 Piano 0 Good 尙 4 Example 8 SP-8 100 - 0 Good Example 9 SP-9 100 _ 0 Good Good Example 10 SP-10 100 • 0 Good Optimum Example Π SP-11 100 • 0 Good Optimum Example 12 SP-12 100 0 Good Excellent - Example 13 SP-13 100 • 0 Good Optimum Example 14 SP-14 100 - 0 Good Example 15 SP-15 100 - 0 Good Optimum Example 16 SP-16 100 - 0 Good Optimum Example 17 SP-17 100 - 0 Good Optimum Example 18 SP-18 100 0 Good Excellent Example 19 SP -10 20 ΡΑ-1 80 Good Excellent Example 20 SP-10 40 ΡΙ-1 60 Excellent Example 21 SP-10 30 ΡΑ-1 35 Good Excellent ΡΙ-1 35 Example 22 SP-16 20 ΡΑ-1 80 Excellent _ _ Example 23 SP-16 40 ΡΙ-1 60 Excellent Excellent Example 24 SP- 16 30 ΡΑ-1 35 Good Excellent ΡΙ-1 35 Example 25 SP-19 100 - 0 Excellent Excellent Example 26 SP-20 100 - 0 Good Excellent Comparative Example 1 - 0 rp-1 100 Good or bad Example 2 7 <Production of retardation film 1> On one surface of a transparent glass substrate, the liquid crystal alignment agent prepared in Example 2 was applied by a spin coater to be prebaked on a hot plate at 80 ° C for 1 minute, and then placed in a box. The film was baked at 200 ° C for 1 hour in a nitrogen displacement oven to form a film having a film thickness of ί. ίμιη. On the surface of the coating film, a Hg-Xe lamp and a Glan-Taylor prism were used to irradiate a polarized ultraviolet light having a wavelength of 3 to 3 nm from a direction perpendicular to the substrate, and a UV filter was used to cut a bright line having a wavelength of 300 nm or less. 0,000 J/m2, a liquid crystal alignment film for producing a retardation film. -54-201206978 Next, on the surface on which the liquid crystal alignment film produced as described above was formed, a polymerizable liquid crystal (Merck's 'RMS03-013C. Filtered by a filter having a pore size of 0·2 μm) was applied using a spin coater, and then 60 Baking on a hot plate at °C for 1 minute, then using a Hg-Xe lamp, irradiating 3 0,0 00]/m2 from the direction of the vertical polymerizable liquid crystal coated surface, containing non-polarized ultraviolet rays having a wavelength of 3 65 nm, and polymerizing The liquid crystal is hardened to produce a retardation film. <Evaluation of retardation film> When the retardation film produced as described above was observed by a polarizing microscope, no abnormal region was observed. Further, the retardation film produced as described above was sandwiched between two polarizing plates disposed on a crossed Nicols, and observed by light (visible light) transmitted in a direction opposite to the observation side. Here, when the liquid crystal alignment film of the retardation film is formed, the polarization direction of the polarized ultraviolet light that irradiates the retardation film is parallel to the polarization direction of one of the polarizing plates, and is sandwiched by an angle perpendicular to the polarization direction of the other block. In the case where the liquid crystal alignment film of the retardation film is formed, the polarization direction of the polarized ultraviolet light to be irradiated is 45 with respect to the polarization directions of the two polarizing plates. When the angle is clamped, the entire surface is observed to be bright, and the retardation film exhibits various kinds of refracting. Example 28 <Production of retardation film having different polarization directions in each region> On one surface of a transparent glass substrate, the liquid crystal alignment agent prepared in Example 2 was applied by a spin coater at 80 ° C On the hot plate, after prebaking for 1 minute, -55-201206978 was post-baked at 200 ° C for 1 hour in a nitrogen gas replacement oven to form a film thickness of Ο.ΐμπι. In a state where half of the surface of the coating film is shielded from light, the first polarized ultraviolet ray is irradiated from the direction perpendicular to the substrate (using a H g - X e lamp and Glan Taylor ella ' to irradiate 10,000 J/m of a bright wire having a wavelength of 313 nm. The first ultraviolet ray is irradiated by using a uv filter to cut off the polarized ultraviolet ray of a bright line having a wavelength of 3 〇 0 nm or less. Next, the exposed portion of the first ultraviolet ray is blocked, and the unexposed portion is rotated by 90 Å from the direction perpendicular to the substrate by the polarized ultraviolet ray irradiated with the first polarized ultraviolet ray. The second polarized ultraviolet ray (using a Hg-Xe lamp and a Glan-Taylor prism, irradiating 10, 〇〇〇J/m2 containing a bright line having a wavelength of 313 nm, and using a UV filter to cut off a polarized ultraviolet ray having a wavelength of 300 nm or less), The second ultraviolet ray irradiation is performed to produce a liquid crystal alignment film for a retardation film. Next, 'on the surface on which the liquid crystal alignment film produced as described above was formed, a polymerizable liquid crystal was applied using a spin coater (Merck, RMS 03-013C, filtered through a filter having a pore size of 0.2 μm), and then at 60 ° C. The hot plate was baked for 1 minute, and then the non-polarized ultraviolet light having a wavelength of 3 65 nm was irradiated from the direction of the vertical polymerizable liquid crystal coated surface by using an Hg-Xe lamp, and the polymerizable liquid crystal was cured. A retardation film having different polarization directions in each region is produced. <Evaluation of retardation film> When the retardation film produced as described above was observed by a polarizing microscope, no abnormal region was observed. -56-201206978 In addition, the phase difference film manufactured as described above is sandwiched between the polarizing plate 1 disposed on the crossed Nicols and the polarizing plate 2, and is observed by light (visible light) transmitted in a direction opposite to the observation side. Here, when the liquid crystal alignment film of the retardation film is formed, the polarization direction of the first polarized ultraviolet ray that irradiates the retardation film is perpendicular to the polarization direction of the polarizing plate 1 and perpendicular to the polarization direction of the polarizing plate 2 At the time of residence (in this case, the polarization direction of the second polarized ultraviolet light is perpendicular to the polarization direction of the polarizing plate 1 and the polarization direction of the polarizing plate 2), the entire surface is observed to be dark, and in contrast, the phase difference is formed. In the liquid crystal alignment film of the film, when the polarization directions of the first and second polarized ultraviolet rays that are irradiated are sandwiched by an angle of 45° with respect to the polarization directions of the two polarizing plates, the regions in which the polarization directions of the radiation are different are the entire surface. Both were observed to be bright, and the retardation film exhibited various refractions. Further, the retardation film produced in the present example was laminated with the retardation film produced in Example 27, and observed with light (visible light) transmitted in the opposite direction to the observation side. Here, in the case where the liquid crystal alignment film of the retardation film of Example 27 is formed, the polarized light direction of the polarized ultraviolet light to be irradiated and the liquid crystal alignment film of the retardation film of the present embodiment (Example 28) are irradiated, the first polarized light is irradiated. When the polarization directions of the ultraviolet rays are superposed in parallel, the exposed portion of the first ultraviolet ray is bright, and the exposed portion of the second ultraviolet ray is observed to be dark, and the liquid crystal of the retardation film of the embodiment 27 is formed. When the polarizing direction of the polarized ultraviolet light to be irradiated when the alignment film is perpendicularly overlaps with the polarization direction of the first polarized ultraviolet light to be irradiated when the liquid crystal alignment film of the retardation film of the present embodiment is formed, the exposed portion of the first ultraviolet irradiation is dark- 57- 201206978, the exposure portion of the second ultraviolet irradiation was observed to be bright. In any of the above cases, the boundaries of the bright and dark regions are clearly edged. Thus, the retardation film of the present embodiment was confirmed to be a retardation film having a different polarization direction in each region. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a conductive film pattern in a substrate having a comb-shaped conductive film used in Examples and Comparative Examples. [Main component symbol description] Charm. </»,, -58-

Claims (1)

201206978 VII. Patent application scope: 1--liquid crystal alignment agent, which is characterized by comprising the following formula (1) (In the formula (1), R is an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a cyano group, respectively, and a is an integer of 〇~4, respectively, and represents a linkage.) 2 A liquid crystal alignment agent of the item 1, wherein the polymer has the above structure in the main chain. 3. The liquid crystal alignment agent of claim 2, wherein the polymer is a reaction product of a polyfunctional epoxy compound containing a diepoxide compound and a polyfunctional carboxylic acid comprising a dicarboxylic acid having the above structure. . A liquid crystal alignment film characterized by being formed of a liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element' is characterized by having a liquid crystal alignment film according to item 4 of the patent application. 6. The liquid crystal display element of claim 5, wherein the liquid crystal display element is a horizontal electric field type liquid crystal display element. 7. A method of forming a retardation film, comprising at least the following steps (a) to (d): (a) coating a liquid crystal on a substrate as in any one of claims 1 to 3 of the patent application. Step of forming a coating film of a polymer by an alignment agent; -59-201206978 (b) a step of irradiating a coating film of the polymer to form a liquid crystal alignment film; (c) applying a polymerizable liquid crystal to the liquid crystal alignment film The step of forming a coating film of a polymerizable liquid crystal, and (d) performing a treatment of a plurality of types selected from the group consisting of heating and irradiation of radiation to cure the coating film of the polymerizable liquid crystal. 8. A retardation film characterized by being formed by the method of item 7 of the patent application. A liquid crystal display element' characterized by having a retardation film as in claim 8 of the patent application. 1 〇 In the case of the liquid crystal display element of claim 9, the liquid crystal display element is used in 3D image display. A polymer comprising the structure represented by the above formula (1). A method for producing a polymer according to claim 11 which is characterized in that a polyfunctional epoxy compound containing a diepoxide compound and a dicarboxylic acid comprising a structure represented by the above formula (1) are used. Acidic polyfunctional carboxylic acid reaction. -60-