TW200944544A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent capable of forming a liquid crystal alignment layer which has good liquid crystal aligning controllability (pretilt angle development of liquid crystal) and of suppressing the accumulation of DC remained during heat-stress pressing which is considered as one of the main reasons of the "burn in" in liquid crystal panel. The above liquid crystal aligning agent comprising a polymer having a specific repeat unit represented by the following formula (1-1), and at least one polymer selected from the group consist of a polyamic acid and an imide polymer thereof, wherein the polyamic acid is obtained by reacting tetracarboxylic dianhydride with diamine. (In formula (1-1), R is hydrogen or methyl group.)

Description

200944544 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film which exhibits excellent liquid crystal alignment control force (pretilt expression performance) and which can suppress residual DC accumulation when thermal stress is applied, and a liquid crystal alignment agent formed of the liquid crystal alignment agent A liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] Since the liquid crystal computer began mass production, liquid crystal display elements have been applied to watches, portable game consoles, word processors, notebook computers, car navigation, etc. from the perspective of space saving and low power consumption. Instruments, camcorders, portable information terminals, digital cameras, mobile phones, various monitors, LCD TVs, etc., and active development continues. As a liquid crystal display element, a TN (twisted nematic) type liquid crystal display element which is continuously twisted by 90 degrees from one substrate to another substrate using a nematic liquid crystal or a long axis of liquid crystal molecules has a higher contrast ratio than a TN type liquid crystal display element. High STN (Super Twisted Nematic) type liquid crystal display elements have been widely used. Further, in order to further improve the display quality of the liquid crystal display, a VA (Vertical Alignment) type liquid crystal display element having a small viewing angle dependency, an IPS (In-Plane Switching) type liquid crystal display element, and a viewing angle of -6-.200944544 have been developed. At the same time, the image is highly responsive to optical compensation bending (optical compensation birefringence = 〇CB) type liquid crystal display elements. In the liquid crystal display element, the member for controlling the liquid crystal alignment is a liquid crystal alignment film. The liquid crystal alignment film is usually formed by applying a liquid crystal alignment agent containing an organic resin to a substrate, then removing the solvent to form a coating film, and rubbing the coating film in a predetermined direction, i.e., "grinding". Here, as the organic resin, polylysine or a ruthenium-based polymer obtained by imidating poly(pyrazine) to give 0 has been widely used, and it has been proposed to contain a previously known poly-proline. Or a method of introducing a large hydrophobic substituent on a polymer side chain when a liquid crystal alignment control force (liquid crystal pretilt angle expression) is produced by a liquid crystal alignment film formed by a liquid crystal alignment agent of a ruthenium iodide polymer (Patent Document 1) ~3). According to this technique, with the introduction of a large hydrophobic substituent, the solubility of the polyaminic acid or its quinone imidized polymer to the solvent is also lowered, and the coating property of the liquid crystal alignment agent is deteriorated. Therefore, there is a need for a new liquid crystal alignment agent capable of producing a liquid crystal alignment φ control force without such a problem. Further, since the liquid crystal alignment film is a member that directly contacts the liquid crystal molecules, it is known that the electrical properties of the liquid crystal alignment film have a very large influence on the burn-in (accumulation of the charge) and the voltage holding ratio of the liquid crystal panel. Therefore, it is expected to improve the burn-in resistance of the liquid crystal panel by improving the liquid crystal alignment film. For example, Patent Document 4 and Patent Document 5 propose a technique in which the accumulated charge is easily diffused by reducing the composition of the liquid crystal alignment film (reduced 200944544 short afterimage erasing time). However, even with this technique, the improvement in burn-in property when applying thermal stress is still not good enough. In recent years, with the application of liquid crystal panels in liquid crystal televisions and advanced monitors, in order to achieve high-quality display performance of liquid crystal alignment films, it is necessary to further improve the performance of the above liquid crystal panels, so that even after long-time driving, Will produce a panel burn-in. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. 6-222366 (Patent Document 7) Japanese Patent Laid-Open No. Hei 6-281937 (Patent Document 8) SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal alignment control force (pretilt performance) which is excellent in display and which is considered to be a liquid crystal panel burn-in. One of the main causes is a liquid crystal alignment agent capable of suppressing the liquid crystal alignment film in which DC is accumulated in the case of thermal stress, a liquid crystal alignment film having the above-described properties, and a liquid crystal display element having excellent burn-in resistance after thermal stress. According to the present invention, the above objects and advantages of the present invention, first, achieved by a liquid crystal alignment agent of 200944544, which comprises a polymer having a repeating unit represented by the following formula - 11) and from a tetracarboxylic dianhydride and a diamine At least one polymer selected from the group consisting of polylysine obtained by the reaction and its quinone imidized polymer,

Ο (In the formula (1), R is a hydrogen atom or a methyl group, and Α1 is a single bond, a phenylene group or a divalent group 圑 represented by the following formula (Α1 - 1) to (Α1 - 5)

-CH2CH2-〇-* (A1-5) (i in equation (A1 - 4) is 0 or 2, and each of equations (A1 - 3), (A1 - 4), and (A1 - 5) indicates its connection The bond is linked to B1) ' & 200944544 is a monovalent organic group having a color skeleton of 9 to 30 carbon atoms). The above objects and advantages of the present invention are attained by a liquid crystal alignment film formed of the above liquid crystal alignment agent, and thirdly by a liquid crystal display element having the above liquid crystal alignment film. According to the present invention, it is possible to provide a liquid crystal alignment of a liquid crystal alignment film which is excellent in coatability and which can exhibit a liquid crystal alignment control force (pretilt performance of liquid crystal) which exhibits excellent display and which can suppress residual DC accumulation when thermal stress is applied. Agent: Liquid crystal alignment film having the above properties: and a liquid crystal display element excellent in burn-in resistance. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention comprises a polymer having a repeating unit represented by the above formula (1) (hereinafter referred to as "polymer (1)") and a polyfluorene obtained by reacting a tetracarboxylic dianhydride with a diamine. At least one polymer selected from the group consisting of aminic acid and its quinone imidized polyruthenium complex. <Polymer (1)> The polymer (1) contained in the liquid crystal alignment agent of the present invention is a polymer having a repeating unit represented by the above formula (1). In the phenylene group of A1 in the above formula (1) or the divalent group represented by the above formula (Α1-〗) to (A1 - 4), the linking position of the linking bond is preferably 4 positions. -10- 200944544 The color full skeleton in B1 of the above formula (1) is a skeleton represented by the following formula.

❹ As the monovalent organic group having 9 to 30 carbon atoms having a colored skeleton, specifically, for example, α-tocopherol, /3-tocopherol, r-tocopherol, 5-tocopherol, etc. may be mentioned. a group derived from a hydroxyl group of the tocol derivative; and a tocotrienol derivative such as α-tocotrienol, no-tocotrienol, r-tocotrienol or tocotrienol The base group obtained by the base. Preferred examples of the repeating unit represented by the above formula (1) include, for example, repeating units each represented by the following formulas (1 to 丨) to (1 - 12).

-11- 200944544

-12- 200944544 (In each of the formulae (1-1) to (1-12), R is the same as the above formula (1)). As R in the above formulas (1 - 1) to (1 - 4), a hydrogen atom or a methyl group is preferably 'as the above formula 0-5'. R' in the formula (1-8) is preferably hydrogen. The atom, as R in the above formula (丨-9)~(1-12), is preferably a methyl group. In particular, it is preferable that the repeating unit ' represented by the above formula (1 - 1) is particularly excellent in that the balance between the pretilt angle expression and the electrical properties is particularly excellent, and it is particularly preferable that r is a methyl group in the above formula (1-1). Repeat unit. In addition to the repeating unit represented by the above formula (1), the polymer (1) may have a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and the following formula (4) At least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (5) and a repeating unit represented by the following formula (6).

(In the formula (2), R' is a hydrogen atom or a methyl group, A2 is a single bond, a methylene group or an alkylene group having 2 to 10 carbon atoms, and B2 is a ring having 2 to 10 carbon atoms. a group of ether structures). 200944544, B3 is hydrogen: and B3 is not a carboxyl group (in the formula (3), R ' ' is a hydrogen atom, a methyl group or a carboxyl group, a methyl group or a carboxyl group, but when R'' is a carboxymethyl group).

(In the formula (4), 'A4 is a single bond, a divalent group containing an oxygen atom, a sulfur or a ruthenium atom, and B4 is an alicyclic group having a carbon number of 4 to 1 Å). Square of atomic and nitrogen atom 6~3 0

(In the formula (5), R''' is a hydrogen atom or a methyl group, a divalent atom of an A5 atom, a sulfur atom, a nitrogen atom or a ruthenium atom; an atom, an alkyl group having 1 to 20 carbon atoms or a aryl group of a carbon atom base). (6) (In the formula (6), 'R,,,' is a hydrogen atom or a methyl group, -C (=〇)-〇-* (wherein the connection with it is a single bond, an oxygen group, B5) The number of hydrogen atoms is 6 to 30. A6 is a single bond or a bond is bonded to B6 to 14-200944544. B6 is an alkylene group having 2 to 10 carbon atoms and an aryl group having 6 to 30 carbon atoms. An alicyclic group having 4 to 10 carbon atoms). The cyclic ether structure contained in the repeating unit represented by the above formula (2)> After the coating film of the liquid crystal alignment agent of the present invention is applied to form a coating film, heat treatment (post-baking) is performed to cause a thermal crosslinking reaction, which can further improve The heat resistance, liquid crystal resistance (solvent resistance), and film density of the obtained liquid crystal alignment agent can further reduce the diffusion of impurity ions contained in the liquid crystal into the liquid crystal alignment film φ, and these effects can be obtained even if the liquid crystal display can be formed. The liquid crystal alignment agent of the liquid crystal alignment film which can reliably solve the voltage retention rate reduction and the burn-in problem by applying thermal stress to the element or driving the liquid crystal panel for a long time, therefore, the polymer (1) preferably has the repetition represented by the above formula (1). a unit and a repeating unit represented by the above formula (2). Therefore, the cyclic ether structure having 2 to 10 carbon atoms in B2 in the above formula (2) is preferably a group containing an epoxyethyl group or an oxetanyl group having thermal crosslinking reactivity. In view of excellent reactivity, it is more preferably an epoxy group. As the repeating unit represented by the above formula (2), it is preferred that A2 in the above formula (2) is a methylene group or an alkylene group having 2 to 10 carbon atoms, and B2 is a group having an epoxy group structure. The repeating unit is more preferably a repeating unit wherein a2 is a methylene group or an alkylene group having 2 or 5 carbon atoms, and B2 is a group having an epoxyethyl structure. In order to improve the compatibility of the polymer (1) with at least one polymer selected from the group consisting of polylysine and its ruthenium imidized polymer, -15-200944544 and when the polymer (1) has In the case of the repeating unit represented by the above formula (2), the polymer (1) may contain a repeating unit represented by the above formula (3) for the purpose of promoting the crosslinking reaction of the cyclic ether structure. In order to further improve the heat resistance of the obtained liquid crystal alignment film, the polymer (1) may contain a repeating unit represented by the above formula (4) or a repeating unit represented by the above formula (5). As A4 in the above formula (4), a single bond is preferred. Examples of the aryl group having 6 to 30 carbon atoms of B4 in the above formula (4) include, for example, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, etc., as a carbon number of 4 to 1 Å. The alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group, and particularly preferably a phenyl group or a cyclohexyl group. As A5 in the above formula (5), a single bond is preferred. Examples of the alkyl group having 1 to 20 carbon atoms of B5 in the above formula (5) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. The aryl group having 6 to 30 carbon atoms may, for example, be a phenyl group, a 4-biphenyl group, a 2-biphenyl group, a 1-naphthyl group or a 2-naphthyl group, and the like. Phenyl. In order to increase the compatibility of the polymer (1) with at least one polymer selected from the group consisting of poly-proline and its ruthenium-imidized polymer, the polymer (1) may be contained in the above formula. (6) Representation of the repeating unit. The alkylene-16-200944544 group having 2 to 1 ring carbon atoms of B6 in the above formula (6) may, for example, be an ethylene group or a 1,4-butylene group; and the carbon number is 6 to 30. The aryl group may, for example, be a phenyl group; and the alicyclic group having 4 to 10 carbon atoms may, for example, be cyclohexane-oxime, 4·diyl or the like. The polymer (1) is a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC), preferably 2 X103 to lx10, more preferably 5 x 10 3 to 5 x 105. Good for 1χΐ〇4~4 0 X105. If the Mw is less than 2x1 03, there is a problem that the elution of the low molecular component causes deterioration of the panel performance (which is a cause of a decrease in the voltage holding ratio or a panel burn-in). On the other hand, when it exceeds 1χ1〇6, the solution viscosity of the obtained liquid crystal alignment agent is too high, and there is a problem in coating properties. Further, the molecular weight distribution (hereinafter referred to as "Mw/Mn" and Μη indicates a polystyrene-equivalent number average molecular weight) is preferably 20.0 or less, more preferably 15.0 or less, and particularly preferably 1 〇. By reducing Mw/Mn ', it is possible to easily obtain a liquid crystal alignment agent which is excellent in coatability and which does not cause deterioration in panel performance due to elution of a low molecular component described above. The polymer (1) as described above can be, for example, a compound represented by the following formula (1 ') (hereinafter referred to as "monomer (1')") or a monomer (1,) and a formula (2) a compound represented by ') (hereinafter referred to as "monomer (2,)"), a compound represented by the following formula (3') (hereinafter referred to as "monomer (3,)"), and the following formula (4') The compound represented by the following (hereinafter referred to as "monomer (4,)"), the compound represented by the following formula (5,) -17-200944544 (hereinafter referred to as "monomer (5,),, ))) and the following formula At least one selected from the group consisting of compounds represented by (6,) (hereinafter referred to as "monomer (6,)"), preferably in a suitable solvent, in the presence of a suitable polymerization initiator Polymerized and synthesized,

(In the formula (1'), R, A1 and B1 are respectively the same as defined in the above formula (1));

(2,) (in the formula (2,), R, A2, and B2 are the same as defined in the above formula (2)); -18- 200944544

CH=CH (3') B3 COOH (in the formula (3'), R" and B3 are the same as defined in the above formula (3));

❿ (In the formula (4'), A4 and B4 are the same definitions as in the above formula (4); R, f / ❿ CH2 = CH (5,) (in the formula (5'), R''' , A5 and B5 are the same definitions as in the above formula (5)); -19- (6, } 200944544 ch2=ch

(In the formula (6'), R''', A6 and B6 are the same as defined above). The monomer (1') is introduced into the above formula (1): body. As a preferable example of the monomer (1'), a compound represented by each of -1) to (1' to 12) may be used. A single enumeration of the repeating unit of S in the above formula (6) is, for example, the following formula (1 ' ch2 = ch c = o ο

(1'-4)

(1-1) (1-2) (1·-3) 20- 200944544

(1,-9) (1-10) (1'-11) (1.-12) (in the formula (1'-1)~(1, a12), R is the same as in the above formula (l) The same definition). -21- 200944544 The monomer (1') can be obtained, for example, by reacting a (meth) propylene hydride halide with a compound B1 - A1-〇H according to a known esterification reaction. The monomer (2') is a monomer to which the repeating unit represented by the above formula (2) is introduced, and specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and 3,4-epoxy acrylate. Butyl ester, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate 0 6 , 7-epoxyheptyl ester and the like. Among them, glycidyl acrylate or glycidyl methacrylate is preferred from the viewpoint of improving the film density of the obtained liquid crystal alignment film and exhibiting excellent electrical properties and reliability of electrical properties. The monomer (3') is a monomer to which the repeating unit represented by the above formula (3) is introduced, and specific examples thereof include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and acrylic acid. , methacrylic acid, crotonic acid, etc., wherein the compatibility between the improved polymer (1) and the polyaminic acid and its quinone imine Q-polymer is good, and the obtained liquid crystal alignment film has a high film density and can be expressed. From the viewpoint of high reliability of electrical properties and electrical properties, acrylic acid or methacrylic acid is preferred. The monomer (4') is a monomer to which the repeating unit represented by the above formula (4) is introduced, and specific examples thereof include fluorenyl-phenylmaleimide, fluorenyl-naphthylmaleimide, and anthracene. - mercapto-maleimide, anthracene-fluorenyl-maleimide, anthracene-cyclopentylmaleimide, anthracene-cyclohexylmaleimide-22-200944544, etc. -phenylmaleimide or N-cyclohexylmaleimide. The monomer (5,) is a monomer which is introduced into the repeating unit represented by the above formula (5)', and specific examples thereof include ethylene, propylene, i-butene, 1-pentene, 1-hexene, and 1- Α-olefins such as heptene, 1-octene, 1-decene, 1-decene, and styrene, 4-vinylbiphenyl, 2-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene And α-methylstyrene, of which φ is preferably styrene. The monomer (6') is a monomer to which the repeating unit represented by the above formula (6) is introduced, and specific examples thereof include isopropenylphenol, methacrylate 2-hydroxyethyl ester, and 2-hydroxyethyl acrylate. , 4-hydroxybutyl acrylate, 1,4-cyclohexane dimethanol monoacrylate, and the like. In the case of synthesizing the polymer (1), the use ratio (copolymerization ratio) of the monomers (1,) to (6,) can be appropriately set depending on the desired composition of the polymer (1). For example, the copolymerization ratio of the monomer (1 ') is preferably 1% by weight or more, more preferably 1 to 60% by weight, still more preferably 2 to 40% by weight, particularly preferably 3, based on the total amount of the monomers. ~30% by weight range. By setting the copolymerization ratio of the monomer (1') within this range, the obtained liquid crystal alignment film can have a good pretilt performance. The copolymerization ratio of the monomer (2') is preferably 50% by weight or less, more preferably 5 to 50% by weight, still more preferably 15 to 45% by weight, particularly preferably 20 to 40% by weight based on the total amount of the monomers. The range of %. By making the monomer (2') -23- Ο

When the copolymerization ratio of 200944544 is within this range, the density of the obtained film can be increased, which can further reduce the diffusion of the liquid crystal alignment film contained in the liquid crystal, thereby further suppressing the liquid crystal burn-in. The copolymerization ratio of the monomer (3') is preferably from 5 to 50% by weight, more preferably from 4 to 50% by weight, even more preferably from 10 to 40% by weight based on the total amount of the monomers. The copolymerization ratio of the monomer to the monomer (2') has a copolymerization ratio of the same monomer (4'), and is preferably 1 to 30% by weight, based on the total amount of the monomers, more preferably 1 to 30% by weight. The range of % by weight. The copolymerization ratio of the monomer (5') is preferably from 1 to 30% by weight based on the total amount of the monomers, more preferably from 1 to 30% by weight, in a range of from 20% by weight. The copolymerization ratio of the monomer (6') is preferably not more than 40% by weight based on the total amount of the monomers, more preferably not more than 40% by weight, and more preferably not more than 1% by weight. As a solvent used in the synthesis of the polymer (1), such as an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether decyl ether, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether, an ethylene glycol ether Acid esters, aromatic hydrocarbons, ketones, esters, and the like. As a specific example thereof, the alcohol may, for example, be a total of 50 Å, preferably 7 to 1 body (3') of the impurity ion of the crystal alignment film to the display element. Preferably, it is 30 > preferably 2~, preferably 30f is preferably 2~, preferably 5 0, preferably 3 0, which may be exemplified by a diethylene glycol alkane ester, a propylene glycol thick, Ethanol, benzyl-24-200944544 alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc.; ethers may include tetrahydrofuran, di-n-pentyl ether, etc.; glycol ethers may, for example, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetate, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, B Glycol monoethyl ether acetate or the like; diethylene glycol alkyl ether; for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether And diethylene glycol ethyl methyl ether, etc.; propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether propionate may, for example, propylene glycol Methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc.; propylene glycol Examples of the alkyl ether acetates include propylene glycol methyl ether oxime acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; and aromatic hydrocarbons include, for example, toluene. And the ketone may, for example, be methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone or the like; and the ester may, for example, be methyl acetate or ethyl acetate. Ester, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, -25- 200944544 2-hydroxy-2-methylpropionate, base Methyl acetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-carbyl Propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid, methoxyacetic acid, methoxy Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl acetoacetate, methyl propoxyacetate, Q propoxyacetic acid Ethyl ester, propoxy propylene acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxyl Ethyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxyl Butyl propyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxy Methyl propionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxy Ethyl propyl propionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like. Among them, preferred are ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and particularly preferably 2-26-200944544 glycol dimethyl ether , diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate or methyl 3-methoxypropionate. As the polymerization initiator to be used in the synthesis of the polymer (1), an initiator generally known as a radical polymerization initiator can be used, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-. Azo-nitride Q compound such as azobis(2,4-dimethylvaleronitrile) or 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); peroxidation An organic peroxide such as benzamidine, lauric acid peroxide, tertiary butyl peroxypivalate, 1,1'-bis(tri-butylperoxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it is also possible to use a peroxide together with a reducing agent as a redox type initiator. In the synthesis of the polymer (1), a molecular weight modifier for adjusting the molecular weight of the polymer (1) can also be used. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; sulfur such as n-hexyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, tertiary dodecanethiol, and mercaptoacetic acid; Alcohols; xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen sulfide; terpinolene, α-methylstyrene dimer, and the like. In the synthesis of the polymer (1), it is preferred to appropriately adjust the polymerization conditions (solvent type, solvent/monomer addition ratio, polymerization temperature, initiator type and amount thereof, molecular weight regulator type, and addition amount thereof, etc.) ), it is controlled within the above molecular weight range. Suitable polymerization conditions for the above range of molecules -27-200944544 are readily known to the skilled person by conducting a small number of preliminary experiments. A polymer solution containing the polymer (1) can be obtained as described above. The polymer solution can be directly used for the preparation of the liquid crystal alignment agent, or the polymer (1) contained in the polymer solution can be separated and used for the preparation of the liquid crystal alignment agent' or the polymer to be separated (1) It is used for the preparation of liquid crystal alignment agent after purification. The separation of the polymer (1) can be carried out by adding the above-mentioned polymer solution to a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure, or decompressing the polymer solution with an evaporator. The distillation method is carried out. Further, the polymer can be purified by a method in which the separated polymer (1) is dissolved again in an organic solvent and then precipitated with a poor solvent or a step of distillation under reduced pressure with an evaporator. ). <Polyamic acid> The polylysine which can be used in the present invention can be obtained by reacting a tetracarboxylic acid Q dianhydride with a diamine. [Tetracarboxylic dianhydride] • As the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid, for example, butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid Dihydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, i,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, iota, 3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-i,2,3,4-cyclobutane Tetracarboxylic acid-28- 200944544 dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4 , 4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3, 4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2 -(:]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo- 3-furyl)·naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethylheptyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]·furan-1,3-two Ketone, l,3,3a,4,5,9b-A hydrogen-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c] -furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-© 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 5-(2,5-dioxo) Tetrahydrofuranyl-3-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxo) Tetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5: 6-dianhydride, 4,9-dioxatricyclo[5.3.1.02'6]-(-alkane-29- 200944544 -3,5,8,10-tetraketone, the following formula - I) or (Τ- II) compound, an aliphatic or alicyclic tetracarboxylic dianhydride represented by;

(wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 and R4 represent a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same or different); pyromellitic dianhydride , 3,3',4,4,-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, iota, 4,5,8-naphthalene Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4,-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' - Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 〇4,4,-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4, 4'_bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3, , 4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene - bis(triphenylphthalic acid) dianhydride, m-phenylene double (three Phenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4,-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4,_diphenyl Methane dianhydride, ethylene glycol-bis(dehydrated trimellitate), propylene glycol - -30- 200944544 bis (dehydrated trimellitate), 1,4-butanediol-bis (dehydrated trimellitate) ), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl) An aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (T-1) to (T-3), propane-bis (dehydrated trimellitate). They may be used alone or in combination of two or more.

Among them, from the viewpoint of enabling liquid crystal alignment which is excellent in performance, it is preferably - butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxyl Cyclopentyl acetic acid dianhydride, 1,3,3 a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-( ;]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydrogen) -2,5-dioxo 0 -3-furanyl)-naphthalene [1,2-indolyl]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3 ,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5'-dione) , 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2- Carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane_3,5,8,1〇-tetraketone, benzene Tetraic acid dianhydride, 3 , 3',4,4'-benzophenonetetracarboxylic dianhydride '3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-biphenyl The tetracarboxylic dianhydride, the 1,4,5,8-naphthalenetetracarboxylic acid phthalic anhydride, and the compound represented by the above formula (τ-I) are represented by the following formulas (T-4) to (T-6). The compound and the compound represented by the following formula (T-7) in the compound represented by the above formula (T-U) (hereinafter collectively referred to as "specific tetracarboxylic dianhydride (1)"). -32- 200944544

Specific examples of the specific tetracarboxylic dianhydride (1) include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1, 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphthalene [1,2-(:]-furan Q-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2 , 4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxane [5.3.1.02'6] undecane-3,5,8,10-tetraketone and pyromellitic dianhydride. -33- 200944544 As a tetracarboxylic dianhydride used in the synthesis of polylysine, It is preferred to use at least one tetracarboxylic dianhydride selected from the group consisting of the above specific tetracarboxylic dianhydrides (1), and the ratio of use of the specific tetracarboxylic dianhydride (1) is relative to all four. a carboxylic acid dianhydride, preferably 1 mole More preferably, it is 10 to 100 mol%. [Diamine] Examples of the diamine used in the synthesis of the above polyamic acid include p-phenylenediamine, m-phenylenediamine, and 4,4'-diamine. Diphenylmethane, 4,4,-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl maple, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 4,4,-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene , 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoro Methyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 5-amino-1-(4'- Aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di(4- Aminophenyl)hexafluoropropane, 2,2-di[4 -(4-Aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3 - bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-1〇-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl- 34- 200944544 -2,7-Diaminoguanidine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3, 3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene Diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2' An aromatic diamine such as bis(trifluoromethyl)biphenyl or 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-φ octafluorobiphenyl; 2,3 -diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium , 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5- Plough, 1,4 -bis(3-aminopropyl) piperene, 2,4-diamino-6-isopropoxy-1,3,5-tri-n, 2,4-diamino- 6-methoxy-1,3,5-three tillage, 2,4-diamino-6-phenyl-1,3,5-tri-trap, 2,4-diamino-6-methyl- s -Tri-trap, 2,4-diamino-1,3,5-tritrap' 4,6-diamino-2-vinyl-s-quinone triple well, 2,4-diamino-5 -Phenylpitrazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-Diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperidinium, 3,6-diamine Acridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, 1 methyl-3,6-diaminocarbazole, 1 ethyl-3,6-di Aminocarbazole, N-phenyl-3,6-diaminosostazole, N,N'-bis(4-aminophenyl)benzidine, a compound represented by the following formula (D-I), - 35- 200944544 h2n

X1-R6 nh2 (DI) (In the formula (D_I), R5 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triterpene, piperidine and piperazine, X1 represents a divalent organic group), a compound represented by the following formula (D-II),

(In the formula (D-II), R6 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of: steep, mouth steep, ternary: piperidine, and piperene, and X2 represents two. a valence organic group, each of which may have the same or different X2 groups; a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amine group; o 1,3-bis(amino group) Methyl)cyclohexane, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-Diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene dimethylene diamine, tricyclo[6.2. 1.02'7] an aliphatic or alicyclic diamine such as undecylenediamine or 4,4'-methylenebis(cyclohexylamine); a diamine group represented by the following formula (D-III) Organic oxane, etc., -36- 200944544 R7 R7 H2N-f CHz^-^i-(-〇-Si-^fCH2-)-NH2 R7 R7 (D-III) (in formula (D-III), R7 A hydrocarbon group having a carbon number of i to i2, and a plurality of R7 groups present may be the same or different, and may be 丨Integer 'q 3 is an integer of 1~20). These diamines may be used alone or in combination of two or more. ® which is preferably p-phenylenediamine, 4,4'-diaminobenzophenone, 4,4,diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diamine Base drug, 4,4,-aminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, i,4-dual ( 4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4,diamino-2,2'-bis(trifluoromethyl) linkage Benzene, 4,4'-diamino-2,2,-dimethylbiphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine® And a compound represented by the following formula (D-1) and a compound represented by the above formula (D-II) in the compound represented by the above formula (D-I), 3,6-diamino acridine; a compound represented by (D-2),

-37- 200944544

H2N

(D-2) 1,3-bis(aminomethyl)cyclohexane, i,4·cyclohexanediamine, 4,4, _methylenebis(cyclohexylamine), the above formula (D - 3,3,-(tetramethyldioxane·1,3-diyl)bis(propylamine) represented by the following formula (D-3) in the compound represented by III),

O ch3 qh3 (D-3) H2N-~(〇H2-)^Sr-〇-Si-fCH2*}jNH2 CH3 ch3 3,6-Diaminocarbazole, N-methyl-3,6-diamine Carbazole, N-ethyl•3,6-diaminocarbazole, N-phenyl·3,6-diaminocarbazole and N,N,-bis(4-aminophenyl)benzidine (Hereinafter, they are collectively referred to as "specific diamines,"). As a more preferable specific diamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,7-diamino fluorene may be mentioned. 4,4'-diaminodiphenyl ether, 4,4,-diamino 2,2,-dimethylbiphenyl and 1,3-bis(aminomethyl)cyclohexane. The diamine used in the synthesis of the polyamic acid is preferably a diamine containing at least one selected from the group consisting of the above specific diamines. In this case, the specific diamine is used in a proportion relative to the entire diamine. More -38- 200944544 is preferably 1 mol% or more, further preferably 10 to 100 mol. /〇β

The liquid crystal alignment agent of the present invention can exhibit a desired pretilt angle by adjusting the composition and content of the above polymer (1) in an appropriate range, and when the liquid crystal alignment agent of the present invention is used for a ruthenium type, In the case of a STN type, OCB type or VA type liquid crystal display element, a diamine used in the synthesis of a polyaminic acid or a quinone imidized polymer contained in a liquid crystal alignment agent is used by using a diamine having a pretilt expression portion. It is also possible to control the pretilt angle of the resulting liquid crystal alignment film. Examples of such a diamine having a pretilt angle expression site include a compound represented by the following formula (D-IV) or a compound represented by the following formula (d-V).

(In the formula (D-IV), R8 and R9 are each independently a hydrogen atom or a methyl group 'R1G is a linear or branched alkyl group having a carbon number of 〜~]〇, and Rm and R12 are each independently two. Valence organic group); r13~r14 Λ (DV) 200944544 (in the formula (D-V), R13 is an oxygen atom, a sulfur atom, -CO-, -COO-, -OCO-, _NHCO_, -CONH. or Methylene, R14 is a monovalent group having a cholestane skeleton or a cholestene skeleton, a monovalent group having a trifluoromethylphenyl group or a trifluoromethoxyphenyl group or a carbon number of 1 to 22 Alkyl). These diamines having a pretilt expression portion may be used alone or in combination of two or more. Specific examples of the compound represented by the above formula (D - IV) include, for example, a compound represented by the following formula (D-4) or (D-5);

Specific examples of the compound represented by the above formula (D-V) include a compound represented by the following formula (D-6) to (D-1). -40- 200944544

When the liquid crystal alignment agent of the present invention is used for a VA type liquid crystal display element, it is preferably represented by the formula (D - V) in the diamine having the pretilt angle expression portion from the viewpoint of exhibiting excellent liquid crystal vertical alignment. As the compound, a compound represented by the above formula (D-6) to (D-10) is more preferably used. The compound represented by the above formula (D-6) or (D-7) is particularly preferably used. The amount of the diamine having a pretilt performance portion is preferably from 8 to 60 mol%, more preferably from 9 to 5 mol%, and particularly preferably from -41 to 200944544, to 10 to 40 mols, based on the entire diamine. %. In this case, a diamine having a pretilt expression portion may be used in combination with the above specific diamine, and the specific diamine is preferably used in an amount of from 1 to 90 mols based on the total of the diamine. /. More preferably 10 to 90% by mole. [Synthesis of Polylysine] The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyamido acid synthesis reaction is preferably tetracarboxylic acid dianhydride relative to 1 equivalent of the amine group contained in the diamine. The acid anhydride group is in a ratio of 0.2 to 2 equivalents, more preferably in a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from 20 to 150 ° C, more preferably at a temperature of from 〇 to 10 ° C. The reaction time is preferably 0.1 to 1 〇 〇 hours, more preferably 1 to 50 hours. The organic solvent which can be used herein is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. , aprotic polar solvents such as N-dimethyl Q-carbamamine, dimethyl hydrazine, τ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-methylphenol, xylenol, A phenolic solvent such as phenol or halogenated phenol. Further, the amount of the organic solvent (a) is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the total amount of the reaction solution (a + b) is 〇. 1 to 30% by weight. the amount. In the above organic solvent, a poor solvent alcohol, a ketone, or an ester of polyglycolic acid may be used in combination in the range in which the produced polyaminic acid is not precipitated. -42- 200944544 ❹

Classes, ethers, halogenated hydrocarbons, hydrocarbons, and the like. When a poor solvent is used in combination with the synthesis of polyamic acid, it is useful for improving the printability of the liquid crystal alignment agent when the obtained polyaminic acid solution is used as it is for the liquid crystal alignment agent. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and lactic acid. Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy propyl Ethyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene Alcohol dimethyl acid, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2, dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, g Alkane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. When the organic solvent and the poor solvent are used in combination, the ratio of use of the poor solvent can be appropriately set within a range in which the produced polyamine acid is not precipitated, and is preferably 70% by weight or less based on the total solvent. More preferably, it is 50% by weight or less. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline acid contained in the anti-43-200944544 solution may be separated and supplied to the liquid crystal alignment agent, or the separated polyfluorene may be prepared. After the acid is refined, the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by introducing the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate by depressurization or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. Further, the poly-proline can be purified by performing the method of redissolving the polyamic acid in an organic solvent once or several times, and then decanting it with a poor solvent or by vacuum distillation using an evaporator. <醯i-Iminylated Polymer> The quinone imidized polymer of polyglycine which can be used in the present invention can be obtained by dehydrating and ring-closing the polylysine obtained as above. The term "indenine-imidized polymer" as used herein means the meaning of a partial sulfimine comprising a partial hydrazide of the above poly-proline and a complete hydrazide of 100% hydrazide, which is hereinafter Collectively referred to as "deuterated polymers". 〇 [tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of the above-imidized polymer' is exemplified by the same compound as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid. The tetracarboxylic dianhydride used in the synthesis of the quinone imidized polymer contained in the liquid crystal alignment agent of the present invention preferably contains a group consisting of an alicyclic tetracarboxylic dianhydride and pyromellitic dianhydride. At least one of the selected -44-200944544 tetracarboxylic dianhydrides. More preferably, 2,3,5·^ residue cyclopentyl acetic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, hydrazine, 3-dimethyl-1, 2,3,4-cyclobutane tetracetic acid dianhydride, 1,3,33,4,5,91>-hexachloro-5-(tetrahydro-2,5-dioxo-3-furanyl)- Naphthalene [1,2-(:]-furan-1,3_diindole, 1,3,3&,4,5,915-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo) _3_咲咲基)-naphthalene [l,2-c]·furan-1,3-dione, 3-oxabicyclo[3 2 Xinyuan-2,4-dione-6-spiro-3 ,-(tetrahydrofuran-2,,5,-dione), 5.(2 5_dioxoindolizin-3-furanyl)-3 -methyl-3-cyclohexene-1,2-diindole Acid liver, 3.5.6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9.dioxatricyclo[5.3.1.02,6]undecane-3, 5,8,10-tetraketone and pyromellitic dianhydride (hereinafter collectively referred to as "specific tetracarboxylic dianhydride (2)"). As a particularly preferable specific tetracarboxylic dianhydride (2), it can be enumerated 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,91)-hexahydro-5-(tetrachloro-2,5-dioxo-3-furanyl)- Naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-/,chloro-8-methyl-5- Nitrogen-2,5- _oxo-3.furanyl)-naphthalene[1,2-C]-furan-1,3-dione, 3-oxabicyclo[3.2.1] 辛院-2 , 4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, 3.5.6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride and 4,9-dioxatricyclo[5.3 .1.02,6]undecane-3,5,8,10-tetraone. As the tetraresidic anhydride used in the synthesis of the ruthenium iodide polymer, at least one tetracarboxylic dianhydride selected from the group consisting of the above specific tetracarboxylic dianhydride (2), preferably selected from the group of _-45-200944544, is preferably used. In this case, the use ratio of the specific tetracarboxylic dianhydride (2) is more preferably 1 mol% or more, and still more preferably 10 to 100 mol%, based on the total tetracarboxylic dianhydride. [Diamine] The diamine used in the synthesis of the above quinone imidized polymer may be the same diamine as the diamine used in the synthesis of the above polyamic acid. 〇 [Synthesis method of ruthenium iodide polymer] The dehydration ring closure reaction of poly phthalic acid can be (i) by heating poly-proline, or by dissolving poly-proline in an organic solvent. The solution is added with a dehydrating agent and a dehydration ring-closing catalyst, and is heated as needed. The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 300 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be sufficiently carried out. If the reaction temperature exceeds 300 °C, the molecular weight of the obtained ruthenium-imided polymer may be lowered. The reaction time is preferably from 2 to 24 hours, more preferably from 3 to 10 hours. On the other hand, in the above method of adding a dehydrating agent and a dehydration ring-closure catalyst to a polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is preferably -46 - .200944544 0.01 to 20 moles relative to the 1 molar acid structure of the polyaminic acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles per 1 mol of the dehydrating agent. In addition, examples of the organic solvent used in the dehydration ring-closure reaction include an organic solvent exemplified as a solvent used in the synthesis of polyamic acid. Further, the reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to ❹ 150 ° C, and the reaction time is preferably 2 to 8 hours, more preferably 3 to 6 hours. The ruthenium iodide polymer obtained in the above method (i) can be directly used for the preparation of a liquid crystal alignment agent, or the obtained ruthenium iodide polymer can be refined and used for a liquid crystal alignment agent. Formulated. Further, in the above method (ii), a reaction solution containing a ruthenium iodide polymer is obtained. For the reaction solution, it can be directly used for the preparation of the liquid crystal alignment agent, or can be used for the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can also separate the ruthenium iodide polymerization Q substance. After it is used, it can be used for the preparation of a liquid crystal alignment agent, or the isolated quinone imidized polymer can be purified and then used for the preparation of a liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as described above for the separation and purification method of polyglycine. - oxime imidization ratio of ruthenium iodide polymer - 47 - 200944544 The ruthenium imidization ratio of the ruthenium iodide polymer used in the present invention is preferably 10 to 99 mol%, more preferably 20 ~99% by mole, especially good for 45~99% by mole. Here, the "rhodium imidization ratio" means the total amount of the structure of the guanidine structure and the number of the quinone ring structure in the ruthenium iodide polymer, and the ratio of the number of the quinone ring structure is expressed as a percentage. Hey. In this case, a part of the quinone ring is an isoindole ring, and is also included in the number of quinone imine structures. The ruthenium imidization ratio can be preferably dried by hydrazine, dissolved in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide), and tetramethyl decane as a reference material. 1H-NMR was measured at room temperature, and it was calculated from the following formula (A) based on the measurement result. Ruthenium amination rate (%) = (1 - A" A2x a ) xl00 (A) A1 = 10 ppm peak area A2 originating from the NH matrix: peak area α derived from other protons: relative to 醯1 ΝΗ ΝΗ ΝΗ ΝΗ , 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚The quinone imidized polymer may be a terminal-modified polymer having a molecular weight adjusted. By using a terminal-modified polymer, the coating property of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. The terminal-modified polymer can be prepared by adding a molecular weight modifier to the polymerization reaction system when the poly-proline acid is in the range of -48 to 200944544. As the molecular weight modifier, for example, a monoanhydride or a monoamine can be cited. The compound, the monoisocyanate compound, etc. Examples of the monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and n-tetradecyl succinic anhydride. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, and anthracene. Amine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The ratio of use of the molecular weight modifier to all tetracarboxylic dianhydrides or all diamines is Preferably, it is 5 mol% or less, more preferably 2 mol% or less. 〇-solution viscosity of polylysine or its quinone imidized polymer prepared as above, when formulated into a solution having a concentration of 20% by weight Preferably, it has a solution viscosity of 500 to 1 〇〇〇〇 mPa.s, more preferably a solution viscosity of 1000 to 7000 mPa's. The solution viscosity (mP a · s) of the above polymer is used for the polymerization. a good solvent (such as N-methyl-2-pyrrolidone, γ-butyrolactone, etc.) is formulated at a concentration of 20% by weight The polymer solution is measured by the Ε-type rotational viscosity -49- 200944544 at 25 ° C. [Use ratio of polyaminic acid and hydrazine imidized polymer] Φ Invented liquid crystal alignment agent from polyamine The ratio of use of at least one polymer selected from the group consisting of acid and ruthenium iodide polymers is preferably such that the weight of the polymer (1) (W1) is different from that of the polyglycolic acid and the ruthenium iodide polymer. The total weight (W2) ratio ^^2=1:99~90:10, more preferably ^:12 = 2:98~80:20, especially for Wi:W2 = 3:97 An amount of ~60:40. <Other Additives> The liquid crystal alignment film of the present invention contains at least one selected from the group consisting of the above polymer (1) and a group consisting of polyglycine and its ruthenium iodide polymer. Essential ingredients, and may also contain other ingredients as needed. Examples of such other components include a functional decane compound, a low molecular compound having two or more epoxy groups in the molecule (hereinafter referred to as "epoxyethyl compound"), and the like. These functional decane compounds or epoxyethyl compounds may be added to the liquid crystal alignment agent of the present invention in order to further improve the adhesion and electrical properties of the resulting liquid crystal alignment film to the surface of the substrate. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxydecane, aminoethyl)-3-aminopropyltrimethoxydecane 'N-(2-aminoethyl-5-200944544)-3-3-aminopropylmethyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-I-propylpropyltrimethoxydecane, Ν-ethoxycarbonyl-3- Aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriethylenetriamine, Ν_trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1 , 4,7-triazadecane, 10-triethoxydecyl-14,7-triazanonane, 9-trimethoxydecyl-3,6-diazadecyl acetate , 9-φ triethoxydecyl-3,6-diazaindolyl acetate, Ν-benzyl-3-aminopropyltrimethoxydecane, Ν-benzyl-3-aminopropyl Triethoxy decane, fluorenyl-phenyl-3-aminopropyltrimethoxy decane, fluorenyl-phenyl-3-aminopropyltriethoxy Alkane, 3-glycidoxypropyltrimethoxydecane, fluorene-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, fluorene-bis(oxyvinyl)-3.aminopropyl Triethoxy decane and the like. When these functional decane compounds are used, the ratio of use thereof is relative to 1 〇〇 by weight of the total amount of the polymer of the present invention (refers to the polymer (1), the poly-proline and the ruthenium poly-Q complex. The total amount, the same applies hereinafter, preferably from 1 to 50 parts by weight, more preferably from 2 to 40 parts by weight, particularly preferably from 3 to 20 parts by weight. Preferred examples of the epoxyethyl compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl-51- 200944544 oil ether, 1, 3,5,6-tetraglycidyl·2,4-hexanediol, N,N,N,,N,-tetraglycidyl-m-xylylenediamine, 1,3-double (N,N_ Diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl_4,4,-diaminodiphenylmethane, Ϊ^Ν,Ν',Ν' - tetraglycidyl p-phenylenediamine, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane or the like. When these epoxyethyl compounds are used, the ratio thereof is preferably from 1 to 60 parts by weight, more preferably from S to 40 parts by weight, based on 100 parts by total of the total amount of the polymer of the present invention, particularly preferably 1 〇~30 parts by weight. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention is at least one selected from the group consisting of the polymer (1), the poly-proline and the ruthenium-imidized polymer thereof as described above, and Other additives which are optionally mixed are preferably dissolved in an organic solvent. The organic solvent which can be used in the liquid crystal alignment agent of the present invention is exemplified by the same solvent as the solvent used in the synthesis reaction of the polymer (1) and the solvent used in the synthesis reaction of polyglycine. The same solvent is exemplified. As a particularly preferable organic solvent to be used in the liquid crystal alignment agent of the present invention, N-methyl-2-pyrrolidone, r-butyrolactone, 7-buteneamine, N,N- may be mentioned from the viewpoint of printability. Dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxy Methyl propionate, ethoxy propionate B-52- 200944544 Ester, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve ), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. They may be used singly or in combination of two or more. © The solvent composition of the liquid crystal alignment agent of the present invention is a composition obtained by combining the above solvents, so that the solid content does not precipitate in the liquid crystal alignment agent and the surface tension of the liquid crystal alignment agent falls to 25 to 40 mN/ The composition of the m range. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, etc., preferably 1 to 50% by weight. More preferably, it is 2 to 40% by weight of 'further preferably 3 to 30% by weight. That is, the liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by applying it to the surface of the substrate and removing the solvent, and when the solid content concentration is less than 1% by weight, the thickness of the coating film will occur. It is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 50% by weight, the thickness of the coating film is too thick to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased, resulting in deterioration of coating properties. It is not possible to obtain a liquid crystal alignment film having an in-plane uniformity of -53-200944544. Further, the particularly preferable solid content concentration range differs depending on the coating method used when the liquid crystal alignment agent is applied to the substrate. More specifically, in order to have an appropriate solution viscosity for each coating method, it is preferred to adjust the liquid crystal alignment agent to a suitable solid content concentration. For example, when the spin coating method is employed, the solution viscosity of the liquid crystal alignment agent is preferably adjusted to a range of 3.0 to 10.0 mPts. When the printing method is employed, it is preferred to adjust the solution viscosity of the liquid φ crystal alignment agent to a range of 12 to 50 mPa's. When the ink jet method is employed, it is preferred to adjust the solution viscosity of the liquid crystal alignment agent to a range of 3 to 15 mPa*s. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above.液晶 The liquid crystal display element of the present invention can be produced, for example, by the following & (1) applying the liquid crystal alignment agent of the present invention to one side of a substrate provided with a patterned transparent conductive film and optionally a reflective electrode by a method such as a roll coating method, a spin coating method, a printing method, or a spray method. Next, 'the solvent is removed by heating the coating surface to form a coating film. Here, as the substrate ', for example, glass such as float glass or soda lime glass; polyethylene terephthalate z-54-200944544 glycol ester, polybutylene terephthalate, polyether maple, polycarbonate, A transparent substrate made of plastic such as alicyclic polyolefin. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, Inc.) made of tin oxide (Sn02), an ITO film made of indium oxide-tin oxide (In2〇3 - SnO 2 ), or the like can be used. The pattern-forming transparent conductive film can be obtained by a method of forming a pattern by photolithography after forming a patterned transparent electrode film on a substrate, or when forming a transparent electrode film, using a pattern having a desired pattern of 0 The method of the mask, etc. For the reflective electrode, a metal such as aluminum or silver or an alloy containing these metals may be used, and as long as it has sufficient reflectance, it is not limited thereto. When the liquid crystal alignment agent is applied, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the reflective electrode and the liquid crystal alignment film, a functional decane compound, a functional titanium compound or the like may be previously coated on the surface of the substrate. After the liquid crystal alignment agent is applied, preheating (prebaking) is usually performed for the purpose of preventing the coating agent liquid from sagging or the like. The temperature of the prebaking Q is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 100 ° C. The prebaking time is preferably from 5 to 10 minutes, more preferably from 0.5 to 5 minutes. Then, a baking (post-baking) step is performed. In the liquid crystal alignment agent of the present invention, the polymer (1) contained in the liquid crystal alignment agent of the present invention contains a cyclic ether structure represented by the above formula (2), except for the purpose of completely removing the solvent from the coating film. The polymer of the repeating unit can also be carried out for the purpose of promoting the thermal crosslinking reaction of the -55-200944544 cyclic ether structure. The latter is preferably 80 to 300 ° C, more preferably 12 0 to 25 (TC. Preferably, the ratio is 5 to 180 minutes, more preferably 10 to 120 minutes, so that a coating film as a liquid crystal alignment film can be formed. The thickness of the coating film is preferably 0.001 to Ιμιη, more preferably 0·5 μηι 0 (2) The surface of the coating film formed as described above by a roll pair of a cloth wrapped with a fiber such as nylon or artificial 0 flower, as needed. Grinding treatment in the direction of friction. In this way, it is possible to control the orientation of the coating film and the pretilt angle control energy, thereby producing a method of controlling the alignment energy by irradiating the surface with ultraviolet light in addition to the method of polishing. Further, the fine powder (foreign matter) generated during the grinding treatment or the like is removed to maintain a clean state, and the formed ruthenium film is preferably washed with a suitable cleaning agent such as at least one selected from the group consisting of isopropyl alcohol and pure water. Further, the liquid crystal alignment film obtained as described above is irradiated with ultraviolet rays to partially illuminate the liquid crystal as shown in the example 6 (JP-A-6-222366) or JP-A-6-281937. The process of changing to a part of the film, or 0.005 〜 fiber, cotton formed by the tempering of the liquid crystal alignment film portion, which is shown in the patent document 8 (Japanese Patent No. 1075 44), is made of a liquid crystal. Split film. In addition, the liquid crystal of the group formed on the surface of the coating film is used as a photoresist film in the group of the surface of the coating film, and the surface is pre-tilted at the surface of the surface of the Japanese alignment film, and the surface is shaped to be -56-200944544. The treatment of removing the photoresist film after grinding in different directions is performed, so that each region of the liquid crystal alignment film has different liquid crystal alignment energy, which can improve the field of view performance of the obtained liquid crystal display element. (3) Two pieces are formed as above. The substrate of the liquid crystal alignment film is placed opposite to each other through a gap (cell gap) so that the polishing direction of the respective liquid crystal alignment films is perpendicular or anti-parallel, and the peripheral portions of the two substrates are bonded together with a sealant to the surface of the substrate and sealed. The cell gap enclosed by the agent is filled with liquid crystal to close the injection hole to form a liquid crystal cell. Then, a polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, the outer surface of each substrate constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a spacer, or the like can be used. Liquid crystal and dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester liquid crystal can be used. , a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, etc. Further, for example, chlorinated bile may be added to these liquid crystals. A cholesteric liquid crystal such as sterol, cholesteryl phthalate or cholesteryl carbonate; a chiral agent sold under the trade names "C-15" and "CB-15" (manufactured by MERCK); Use of a ferrous-p-amino-2-methylbutyl cinnamate, etc., -57-200944544, ferroelectric liquid crystal, etc. As a polarizing plate bonded on the outer surface of a liquid crystal cell, the polyvinyl alcohol is extended and aligned. A polarizing plate obtained by absorbing iodine, which is referred to as a "ruthenium film", is sandwiched between a protective film of cellulose acetate, or a polarizing plate made of a ruthenium film itself. [Examples] Hereinafter, the present invention is further carried out by way of examples. Specific description, but 0 is the invention and not Limited to these examples. Measurement of solution viscosity, weight average molecular weight, and molecular weight distribution of polymers in the examples and comparative examples, evaluation of vertical alignment of liquid crystal display elements, voltage holding ratio, and burn-in resistance of liquid crystal display elements The following procedure was carried out: [Measurement of solution viscosity] The solution viscosity (mPa's) of the polymer, _ the polymer solution indicated in each synthesis example was measured at 25 ° C using a 旋转-type rotary viscometer. Measurement of weight average molecular weight and molecular weight distribution] The weight average molecular weight (Mw) and the number average molecular weight (?η) in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions to obtain a molecular weight distribution (Mw/Mn). GPC measuring device: "HLC-8020" manufactured by Tosoh Co., Ltd. Column: TSK guardcolum α manufactured by Tosoh, -58- 200944544 TSK gel α-Μ and TSK gel α-2500 are connected in series use. Solvent: 9.4 g of lithium bromide monohydrate and 1.7 g of a solution of phosphoric acid dissolved in 3 L of dimethylformamide. Measurement temperature: 35 °C. [Production of Liquid Crystal Display Element] The liquid crystal alignment agent prepared in each of the examples or the comparative examples was applied onto a transparent conductive ruthenium film made of an ITO film provided on one surface of a glass substrate by a spin coater at 80 ° C on a hot plate. After prebaking for 1 minute, it was baked in a clean oven (under a nitrogen atmosphere) at 200 ° C for 1 hour to obtain a substrate on which a coating film having a film thickness of 60 nm was formed on the transparent conductive film. The substrate was subjected to a sanding treatment at a roller speed of 400 rpm, a table moving speed of 30 mm/sec, and a fluffing length of 0.4 mm, using a sanding machine equipped with a roller of rayon cloth. The film produces liquid crystal alignment energy. Then, the substrate was ultrasonically washed in pure water for 1 minute, and then dried in a clean oven at 100 °C for 10 minutes to prepare a substrate having a liquid crystal alignment film. These operations were repeated to produce a pair of (two pieces) substrates having a liquid crystal alignment film. Then, on each outer edge of the surface of the pair of liquid crystal alignment films having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to form a liquid crystal alignment film surface. The pressure is relatively heavy and combined, and the adhesive is cured. Next, after negative-type liquid crystal-59-200944544 (MLC-2038, manufactured by MERCK Co., Ltd.) was filled into the substrate gap through the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocurable adhesive on both outer sides of the substrate. A polarizing plate is bonded to produce a vertical alignment type liquid crystal display element. [Evaluation of the vertical alignment property] The vertical alignment type liquid crystal display device manufactured as described above was measured for the pretilt angle by using the anchor strength measuring device "OMS_J3" manufactured by Central Seiki Co., Ltd., and the pretilt angle was 87 or more. The evaluation was “good Q”, and the vertical alignment was evaluated as “bad” below 8 7 °. [Evaluation of voltage holding ratio] A voltage of 5 V was applied to the liquid crystal display element manufactured as above at 60 ° C for a time span of 1,670 msec, the voltage application time was 60 μsec, and then at 60 ° C. The voltage holding ratio after the voltage was released to 1 670 msec was measured. The voltage holding ratio measuring device was VHR-1 manufactured by TOYO Corporation. If the 保持 of the voltage holding ratio is 97.5% or more, the voltage holding ratio is rated as "good", and if it is less than 97.5%, 〇 is rated as "failed". [Evaluation of the burn-in resistance (measurement of residual DC voltage)] After applying a DC voltage of 18 V for 17 hours to the liquid crystal display element manufactured as above in an environment of 100 ° C, the application of the voltage was released, and the room temperature was applied. After the attenuation for 15 minutes, the residual voltage (residual DC voltage) in the liquid crystal cell was determined by the scintillation elimination method. When the residual DC voltage is small, it can be judged that it is a liquid crystal display element excellent in burn-resistant property. Residual DC voltage • 60- 200944544 液晶 is a liquid crystal display element of 500mV or less, and the burn-in resistance can be rated as “good”. When the residual DC voltage 値 is higher than 500mV, the burn-in resistance can be evaluated as “failed”. Synthesis Example 1 (Synthesis (1) of Compound (1)) Tocopheryl methacrylate was synthesized according to the following Reaction Scheme 1.

Reaction Scheme 1 89 g of α-tocopherol was dissolved in 800 ml of dehydrated tetrahydrofuran (THF). After adding 27 g of triethylamine, 36 g of methacrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 3 hours to carry out a reaction. After completion of the reaction, triethylamine hydrochloride was removed by filtration, and THF was evaporated under reduced pressure. The solution was washed with water, and the organic layer was dried over magnesium sulfate. chloroform was evaporated under reduced pressure to obtain 85 g of the desired product y-y- phenolic acid methacrylate (yield: 83%). Synthesis Example 2 (Synthesis (2) of Compound (1')) Tocopheryl acrylate was synthesized according to the following Reaction Scheme 2. -61- 200944544

In the above-mentioned Synthesis Example 1, 80 g of the target product α-tocopheryl acrylate (yield: 80%) was obtained in the same manner as in Synthesis Example 1 except that 32 g of acrylonitrile chloride was used instead of methyl hydrazine chlorochloride. Synthesis Example 3 (Synthesis of Polymer (1) (1))

To a four-necked flask equipped with a stir bar, a three-way valve, and a thermometer, 33 g (0_066 mol) of methacrylic acid methacrylate prepared in the above Synthesis Example 1 as a monomer, glycidol methacrylate was added. Base ester 25g (0.18 mole), methacrylic acid 14g (0.16 mole), styrene 7.〇g (0.067 mole), N-cyclohexylmaleimide 7.0g (0.039 寞) and methyl 2 g of 2-hydroxyethyl acrylate (0.11 mol), and then added 200 g of diethylene glycol ethyl methyl ether as a solvent, 2,2'-azobis(2,4-dimethylpentene) as a polymerization initiator Nitrile) 4.58 and 2.0 g of α-methylstyrene dimer as a molecular weight modifier. This was bubbled with a nitrogen stream for about 1 minute, nitrogen gas in the system was ventilated, and then reacted under nitrogen atmosphere at -62-200944544 at 70 ° C for 5 hours to obtain 32% by weight of a polymer ( 1 - 1) solution. The molecular weight of the polymer (1-1) was measured by GPC, Mw = 24000, Mw/Mn = 2.4, and no peak derived from residual monomers was identified. Synthesis Example 4 (Synthesis (2) of Polymer (1)) In the above Synthesis Example 3, in place of methacrylic acid, α-tocopherol 33 g (0.06 8 mol) obtained in the above Synthesis Example 2 was used. In the same manner as in Synthesis Example 3 except for the use of the tocopherol, a solution containing 33% by weight of the polymer (1-2) was obtained. The polymer (1 - 2) was subjected to molecular weight measurement by GPC, Mw = 26000, and Mw / Mn = 2 - 5, and no peak derived from the residual monomer was identified. Synthesis Example 5 (Synthesis of Polylysine (1)) 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid diphenyl as a tetracarboxylic dianhydride, and as a diamine compound 2,2,-Dimethyl-4,4'-diaminobiphenyl 212g (l. oxime) is dissolved in a mixed solvent consisting of 37 〇g N methyl 2_ 0 pyrrolidone and 3300 gy-butyrolactone The reaction was carried out at 40 ° C for 3 hours to obtain about 4070 g of a solution containing 1% by weight of poly-proline (PA-1). The solution viscosity of the polyaminic acid solution is 16 (mPa.s). Synthesis Example 6 (synthesis of poly-proline (2)) 3,4-cyclobutane tetracarboxylic acid as tetracarboxylic dianhydride Dianhydride 98g (0.50 mole) and pyromellitic dianhydride 1〇9g (〇5〇莫耳), and -63-.200944544 4,4'-diaminodiphenylmethane 198g as diamine compound (l. 〇mol) was dissolved in a mixed solvent consisting of 230 g of N-methyl-2-pyrrolidone and 2060 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours, and then added 1 3 50 g of γ- Butyrolactone gives about 4040 g of a solution containing 10% by weight of poly(A). The polyglutamic acid solution has a solution viscosity of 125 mPai. Synthesis Example 7 (Synthesis of Polylysine (3)) 均 9 g of pyromellitic dianhydride as a tetracarboxylic dianhydride (0.50 mol and 1,2,3,4-cyclobutane tetracarboxylate) Acid dianhydride 98 g (0.50 mol), and 4,4-diaminodiphenyl ether 20 (^ (mole) as a diamine compound are dissolved in 230 g of N-methyl-2-pyrrolidone and In a mixed solvent of 2060 g of Y-butyrolactone, after reacting at 40 ° C for 3 hours, 135 μg of γ-butyrolactone was added to obtain about 4040 g of 10% by weight of polyglycine (PA-3). The solution has a solution viscosity of 200 mP a·s. 〇Synthesis Example 8 (Synthesis of ruthenium iodide polymer (1)) 2,3,5-three as tetracarboxylic dianhydride 21 g (0.094 mol) of carboxycyclopentyl acetic acid dianhydride, 9.2 g (0.085 mol) of p-phenylenediamine as a diamine compound, and 4.9 g (0.0094 mol) of a compound represented by the above formula (D-6) The reaction was carried out in 14 〇g N-methyl-2-pyrrolidone at 60 ° C for 5 hours to obtain a solution containing 20% by weight of polyglycolic acid. The solution viscosity of the solution was 2400 mP as. -64- 200944544 Add 3 25 g of N-methyl-2-pyrrolium to the polyamic acid solution _ (NMP) 'Additional 7.4g of pyridine and 9.5g of acetic anhydride, 4 hours of dehydration ring closure reaction at ll (TC). After dehydration ring closure reaction, solvent replacement by solvent in the system with new NMP (in this operation) The pyridine and acetic anhydride used in the hydrazine imidization reaction were removed to the outside of the system. The same as above, a ruthenium iodide polymer (PI-1) containing 15% by weight of ruthenium iodide was about 51%. A polymer solution was taken. A small amount of the polymer solution was taken and diluted with NMP to a solution having a polymer concentration of 7.7% by weight, and the solution viscosity was determined to be 22 mPa·s. Synthesis Example 9 Synthesis of a ruthenium-based polymer (2) 19 g (0.0 8 5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 7.3 g of p-phenylenediamine as a diamine compound (〇.〇) 68 摩尔) and 8.9 g of the compound represented by the above formula (D-6) are dissolved in 140 g of N-methyl-2-pyrrolidone (NMP) for 5 hours at 60 ° C. A polyphthalamide-containing poly ruthenium solution is obtained. A small amount of the solution is added, NMP is added, and a solution having a polymer concentration of 20% by weight is prepared, and the solution is dissolved. The viscosity was 2200 mPa's. To the polyamic acid solution, 325 g of N-methyl-2-pyrrolidone (NMP) was added, and 7.3 g of pyridine and 9.4 g of acetic anhydride were added thereto, and dehydration was carried out at ll ° C for 4 hours. Closed-loop reaction. After the dehydration ring-closing reaction, the solvent in the system was replaced with a new NMP solvent to obtain a ruthenium iodide polymer (PI-2) containing 15% by weight of ruthenium iodide ratio of about 50%. Poly-65- 200944544 compound solution. A small amount of the polymer solution was taken and diluted with NMP to a solution having a polymer concentration of 7.7% by weight, and the solution viscosity was determined to be 22 mPai. Synthesis Example 10 (Synthesis of a ruthenium iodide polymer (3)) 21 g (0.094 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride as a diamine compound 5.2 g (0.085 mol) of p-phenylenediamine and 4.7 g (0.0095 mol) of the compound represented by the above formula (D-7) were dissolved in 140 g of N-methyl-2-pyrrolidone (NMP) at 60 ° C. The reaction was carried out for 5 hours to obtain a solution containing 20% by weight of polyamic acid. The solution has a solution viscosity of 5800 mPai. To the polyamic acid solution, 325 g of N-methyl-2-pyrrolidone (NMP) was added, and 7.4 g of pyridine and 9.6 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent to obtain a polyfluorene containing 15% by weight of a ruthenium iodide polymer (PI-3) having a ruthenium iodide ratio of about 53%. Solution. A small amount of the polymer solution was taken and diluted with NMP to a solution having a polymer concentration of 7.5% by weight, and the solution viscosity was determined to be 40 mPa_s. Synthesis Example 11 (Synthesis of a ruthenium iodide polymer (4)) 19 g (0.085 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, as a diamine compound Benzene diamine 7.4g (0_068 mole) and the compound represented by the above formula (D-7) -66-200944544 8.5g (0.017 mole) are dissolved in 140g of N-methyl-2-pyrrolidone (NMP), The reaction was carried out for 5 hours at 60 ° C to obtain a solution containing 20% by weight of polyamic acid. The solution has a solution viscosity of 5300 mPa-s. To the polyamic acid solution, 325 g of N-methyl-2-pyrrolidone (NMP) was added, and 6.7 g of pyridine and 8.7 g of acetic anhydride were further added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent to obtain a polymer containing 15% by weight of a ruthenium iodide polymer (PI-4) having a ruthenium iodide ratio of about 51%. Solution. A small amount of the polymer solution was taken and diluted with NMP to a solution having a polymer concentration of 7.5% by weight, and the solution viscosity was determined to be 39 mPa·s. Synthesis Example 12 (Synthesis of a ruthenium iodide polymer (5)) 20 g (0.089 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride as a diamine compound Phenylenediamine 6.8 g (0.063 mol), compound O represented by the above formula (D-6) 4.7 g (0.0090 mol) and 4,4'-diaminodiphenylmethane 3.6 g (0.018 mol) The solution was dissolved in 140 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C for 4 hours to obtain a solution containing 20% by weight of polyglycine. The solution has a solution viscosity of 2400 mP a.s. To the polyamic acid solution, 325 g of N-methyl-2-pyrrolidone (NMP) was added, and 14 g of pyridine and 18 g of acetic anhydride were further added thereto, and dehydration ring closure was carried out for 4 hours at ll 〇 °cf. After the dehydration ring closure reaction, the solvent was replaced with a new γ-butyrolactone in a solvent of -67-, 200944544 in the system to obtain a ruthenium iodide polymer containing 15% by weight of ruthenium iodide (about 78%). ΡΙ - 5) polymer solution. A small amount of the polymer solution was taken, and γ-butyrolactone was added to dilute to a solution having a polymer concentration of 6.5% by weight, and the solution viscosity was measured to be 21 mP a·s. Comparative Synthesis Example 1 (Synthesis of Comparative Polymer) To a four-necked flask equipped with a stir bar, a three-way valve, and a thermometer, 40 g (0.28 mol) of glycidyl methacrylate as a monomer was added. 20 g (0.23 mol) of methacrylic acid, 20 g (0.19 mol) of styrene and 20 g (0.11 mol) of N-cyclohexylmaleimide, and then 200 g of diethylene glycol ethyl methyl ether as a solvent. 2,2'-azobis(2,4-dimethylvaleronitrile) 4.5 g as an initiator and 2.0 g of α-methylstyrene dimer as a molecular weight modifier. This was bubbled with a nitrogen stream for about 1 minute, nitrogen gas in the system was ventilated, and then reacted at 70 ° C for 5 hours under a nitrogen atmosphere to obtain a comparative polymer containing 33% by weight (R 〇-1). a polymer solution. The molecular weight of the polymer (R-1) was determined by GPC! ^==22000 » Mw/Mn = 2.4 - No peaks were detected for residual monomers. Example 1 The solution containing the polymer (1) and the solution containing polylysine (pa-1) prepared in the above Synthesis Example 5 were prepared in the above Synthesis Example 3 to give a polymer (1 to 1). / / polymer (PA ~ 1) weight ratio of 30/70 -68- 200944544 mixed, adding N-methyl-2-pyrrolidone (NMP) and butyl cellosolve to prepare the solvent composition of NMP / butyl solution Fibrous agent / 7*-butyrolactone / diethylene glycol ethyl methyl ether = 23 / 50 / 25 / 2 (weight ratio), a solid content concentration of 3.5% by weight of the solution. After the solution is fully stirred, the pore size The liquid crystal alignment agent was prepared by filtration through a 0.2 μm filter. The liquid crystal alignment agent was used for evaluation according to the above method. The evaluation results are shown in Table 1. Example 2 The polymer-containing product obtained in the above Synthesis Example 3 was used. The solution and the solution containing poly-proline (pa-1) prepared in the above Synthesis Example 5 were mixed so that the weight ratio of the polymer (1:1)/polymer (PA-1) was 30/70. 10 parts by weight of ruthenium, osmium, Ν', Ν'-four as an epoxy compound are added thereto in relation to the total amount of 100 parts by weight of the polymer. Glycidyl-m-xylylenediamine. Further, yttrium-methyl-2-pyrrolidone© (ΝΜΡ) and butyl cellosolve were added to prepare a solvent composition of ΝΜρ/butyl cellosolve/r-butyrolactone/digan Alcohol ethyl methyl ether = 23/50/2 5 /2 (weight ratio), a solution having a solid content concentration of 3.5% by weight. After the solution was thoroughly stirred, it was filtered with a filter having a pore size of 〇·2 μΓη to prepare a liquid crystal. The liquid crystal alignment agent was used for evaluation according to the above method. The evaluation results are shown in Table 1. -69 - 200944544 Examples 3 to 5, Example 9, and Example 12 In the above Example 1, except for use The liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 1 except that the type and amount of the polymer and the solvent composition were as shown in Table 1. The evaluation results are shown in Table 1. Examples 6 to 8 and Example 1 1, 1 , Example 1 3 to 18, Comparative Examples 1 and 2 In the above Example 2, in addition to the kind and amount of the polymer used, the epoxy compound (Ν, Ν, Ν ', Ν ' - tetraglycidyl-m-xylylenediamine) and solvent composition as shown in Table 1. The liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 2. The evaluation results are shown in Table 3. Comparative Example 3 The solution containing the quinone imidized polymer (PI-1) prepared in the above Synthesis Example 8. N-methyl-2-pyrrolidone (NMP) and butyl cellosolve 6 were added for dilution to prepare a solution having a solvent composition of NMP/butyl cellosolve = 50/50 (weight ratio) and a solid content concentration of 3.5% by weight. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent. _ Using the liquid crystal alignment agent, evaluation was carried out in accordance with the above method. The results of the evaluation are shown in Table 1. Comparative Example 4 -70-200944544 To 5 parts by weight of the polymer, 5 parts by weight of a ruthenium compound as an epoxy group was added to the solution of the ruthenium-imidized polymer (PI-1) prepared in the above Synthesis Example 8. , Ν, Ν ', Ν '-tetraglycidyl-m-xylylenediamine, and then added N_methyl-2-pyrrolidone (NMP) and butyl cellosolve to dilute, formulated into a solvent composition of NMP / butyl solution A solution of 5 0/5 0 (by weight) and a solid content concentration of 3.5% by weight. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a Q-out liquid crystal alignment agent. The liquid crystal alignment agent was used and evaluated in accordance with the above method. The results of the evaluation are shown in Table 1. Comparative Examples 5 to 7 In the above Comparative Example 4, a liquid crystal alignment agent was prepared and evaluated in the same manner as in Comparative Example 4 except that the type of the polymer and the amount of the epoxy group compound were as shown in Table 1. The evaluation results are shown in Table 1. Comparative Example 8 10 10 parts by weight of a hydrazine as an epoxy group was added to a solution of the quinone imidized polymer (ΡΙ - 5 ) prepared in the above Synthesis Example 12 with respect to 1 part by weight of the polymer. Ν,Ν'Ν'-tetraglycidyl-m-xylylenediamine, and then added γ-butyrolactone, Ν-methyl-2-pyrrolidone (ΝΜΡ) and butyl cellosolve to dilute to form a solvent group A solution having γ_butyrolactone/ΝΜΡ/butyl cellosolve=40/30/40 (weight ratio) and a solid content concentration of 3.9 wt%. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of -71 to 200944544 of 0.2 μm to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was used and evaluated in accordance with the above method. The results of the evaluation are shown in Table 1.

-72- 200944544

Qo Liquid crystal display element with burn-in resistance residual DC voltage (mV) 〇Ο (Ν »·Ή Ο ΓΛ ί—Μ § ο »—Η § Voltage holding ratio (%) 〇6 〇\ 00 Os Os Ο) On Ο 00 On CN 〇6 On ΟΟ σ Ό ΟΟ ΟΝ <Ν οό Ον cn od ON Ο 00 ON ο Os as (N 〇\ pretilt 〇〇 \ SS inch 00 00 ΟΟ 00 00 5 00 <N 〇d 00 inch 00 00 κη 〇6 00 to 00 00 Liquid crystal alignment agent Solvent composition (weight ratio) NMP/BC/BL/EDM=23/50/25/2 NMP/BC/BL/EDM=23/50/25/2 NMP/ BC/BL/EDM=23/50/25/2 NMP/BC/BL/EDM=23/50/25/2 NMP/BC/BL/EDM=23/50/25/2 NMP/BC/EDM=49.6 /50/0.4 NMP/BC/EDM=49.6/50/0.4 NMP/BC/EDM=49/50/l NMP/BC/EDM=49.6/50/0.4 NMP/BC/EDM=49.6/50/0.4 NMP/ BC/EDM=48/50/2 NMP/BC/EDM=49.6/50/0.4 NMP/BC/EDM=49.6/50/0.4 For example _ 酹 _ 1 S'1 Vw/ 1 1 1 δ δ δ 1 δ s 1 polymer surface enthalpy) Polymer-2 PA-1 (70) -! PA-1 (70) PA-2 (70) PA-3 (70) PA-1 (70) PI-1 ( 95) ΡΙ-2 (95) ΡΙ-2(85) PI-3 (95) PI-3 (95) PI-3 (80) PI-4 (95) PI-4 (95) Polymer-1 Polymer 1-1(30) Polymer 1-1(30) Polymer Bu 1(30) Poly Compound 1-1 (30) Polymer 1-2 (30) Polymer 1-1 (3) Polymer 1-1 (5) Polymer 1-1 (15) Polymer 1-1 (5) Polymer 1-1 ( 5) Polymer 1-1 (20) Polymer 1-1 (5) 1 Polymer 1-1 (3) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 - £L - 200944544

(Puffin) I撇οQ Liquid crystal display element with burn-in resistance residual DC voltage (mV) 〇Ο ro Ο 1—Η Η Ο ο o (N (N o oo o 〇oo oo Ο 00 Ο (N voltage retention rate (% ) 00 〇〇〇\ (N a; On w^> 00 Os οο οό ο ο On On ο as On On Q Q\ oo vd Os 00 ON o si inch od Ο m od Os shape 00 00 Ό 00 00 m Οό οο 00 00 inch CN OO o oo *r> od oo 〇\ 00 o ss 呀 00 Liquid crystal alignment agent solvent composition (weight ratio) NMP/BC/EDM=49/50/l NMP/BC/BL/EDM= 9.6/40/50/0.4 NMP/BC/EDM=49/50/l NMP/BC/EDM=49/50/l NMP/BC/BL/EDM=9/40/50/l NMP/BC/EDM= 49.3/50/0.7 NMP/BC/BL/EDM=9.3/40/50/0.7 NMP/BC=50/50 NMP/BC=50/50 NMP/BC=50/50 NMP/BC=50/50 NMP/ BC=50/50 NMP/BC/BL=10/40/50 Epoxy compound (parts by weight) δ δ s δ δ ss 1 δ s δ Polymer surface (parts by weight) Polymer-2 PI-4 (85 PI-5 (95) PI-2 (85) ΡΙ-4 (85) PI-5 (85) PI-1 (90) PI-5 (90) 1 1 1 1 1 1 Polymer-1 Polymer 1 -1(15) Polymer 1-1(5) Polymer 1-2(15) Polymer 1-2(15) Polymer 1-2(15) R-1(10) Rl(10) PI-1 (100) PI-1(100) PI-2(100) P Bu 3(100) PI 4(100) PI~5(100) Example 14 Example 15 Example 16 Example 17 Example 18 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 _ Inch/-, 200944544 wherein the abbreviations in the solvent composition column of Table 1 have the following meanings: NMP : N-methyl-2-pyrrolidone BC: butyl cellosolve (ethylene glycol monobutyl ether) EDM : diethylene glycol Ethyl methyl ether BL: γ-butyrolactone From the above Table 1, it is understood that the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can simultaneously achieve excellent liquid crystal alignment control force (especially vertical alignment) and high voltage retention. All properties of rate and good burn-in resistance (actual examples 1 to 18). On the other hand, the liquid crystal alignment film formed of the liquid crystal alignment agent previously known cannot satisfy all of the above properties at the same time (Comparative Examples 1 to 8). The liquid crystal display element of the present invention having the liquid crystal alignment film as described above exhibits excellent performance. The liquid crystal alignment control force (especially the vertical alignment property) can suppress the accumulation of residual DC when thermal stress is applied, and the liquid crystal display element has an advantage of reducing burn-in. [Simple description of the diagram] 0 None. [Main component symbol description] 4τγγ None. -75-

Claims (1)

200944544 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by comprising: a repeating unit of a polymer and a group c compound from the group consisting of tetracarboxylic dianhydride and diamine and醯i-imidized polymer composition, (f \ -4-ch2-c-4- (1) c=o I ο Ο too 1 In formula (1), R is a hydrogen atom or a methyl group, and Α1 is a formula j ( The monovalent organic 3 (A1-1) having a carbon number of 9 to 30 in the divalent group represented by A1 to 1) to (A1 - 5) has the following formula (1): at least one selected polycondensation Polyphthalic acid bond, phenylene or the following, B1 is a color-filled bone group, €> (A1-2) (A1 is a value of 0 or 2 in the formula (A1 - 4), and each of the formulas (A1 - 5) represents a connection bond thereof and 2. a liquid crystal alignment as in the first item of the patent application - 3), (A1) — 4) and (A1 B1 are connected. 丨, wherein the repeating unit shown by the above formula (1), Table-76-200944544 is a repeating unit represented by the following formula (1_丨) (1-1) ’ In the formula (1~1), 'R is synonymous with R in the above formula (1). The liquid crystal alignment agent according to claim 1 or 2, wherein the polymer having the repeating unit represented by the above formula (1) further has a repeating unit represented by the following formula (2), Q CH, ο ==丨21 CM •oo & (2) In the formula (2), 'R is a hydrogen atom or a methyl group, and a2 is a single bond, a methylene group or an alkylene group having a carbon number of 2 to 1 Å. Β2 has a carbon atom. A group of a cyclic ether structure having a number of 2 to 1 Å. 4. The liquid crystal alignment agent of claim 3, wherein the oxime in the above formula is a group having an epoxyethyl structure or an oxetanyl structure. -77-200944544 5. The liquid crystal alignment agent of claim 4, wherein A2 in the above formula (2) is a methylene group or an alkylene group having 2 to 10 carbon atoms, and B2 has an epoxy group. The group of the structure. 6. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein at least one polymer selected from the group consisting of polylysine and its quinone imidized polymer is the following tetracarboxylic acid At least one polymer selected from the group consisting of polyphthalic acid and its quinone imine polymer obtained by reacting an acid dianhydride with a diamine containing 2, 3, 5 - Tricarboxycyclopentyl hydrazine acetic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3 -dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid Anhydride, 1,3,3&,4,5,91>-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-<:]- Furan-1,3-dione, l,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2', 5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6 -tricarboxy-2-carboxynorbornane - 2:3,5:6-dianhydride, 4,9-dioxa-3-tricyclo[5.3丄〇2'6]undecane-3,5,8, 10-four And at least one selected from the group consisting of pyromellitic dianhydride, the diamine comprising p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,7-diaminopurine, 4, a group consisting of 4'-diaminodiphenyl ether, 4,4'-diamino-2,2,-dimethylbiphenyl and 1,3-bis(aminomethyl)cyclohexane At least one of the selected ones. 7. The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the diamine is a diamine containing a compound represented by the following formula (D-V), -78-200944544 p13-p!4 X (DV) Wy h2n nh2 In the formula (D-V), R13 is an oxygen atom, a sulfur atom, -CO-, -COO-, -OCO-, -NHCO-, -CONH- or methylene, and R14 is a bile A monovalent group of a brothel skeleton or a cholestene skeleton, a monovalent group having a trifluoromethylphenyl group or a trifluorofluoromethoxyphenyl group or an alkyl group having 1 to 22 carbon atoms. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 7. A liquid crystal display element having a liquid crystal alignment film according to item 8 of the patent application. ❹ -79- 200944544 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: