TW201827576A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent which is characterized by containing an organic solvent and at least one polymer selected from among polyamic acids and imidized polymers of polyamic acids, said polyamic acids being obtained using tetracarboxylic acids that contain a tetracarboxylic acid dianhydride represented by formula (1) and an aliphatic tetracarboxylic acid dianhydride at a ratio of from 10:90 to 90:10 and diamines that contain a diamine represented by formula (2).

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the liquid crystal display element.

[0002] Conventionally, liquid crystal devices have been widely used in display portions of personal computers, portable phones, video receivers, and the like. The liquid crystal device includes, for example, a liquid crystal layer sandwiched between the element substrate and the color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls alignment of liquid crystal molecules of the liquid crystal layer, and an opening and closing. A thin film transistor (TFT) or the like that supplies an electrical signal to a pixel electrode. For the driving method of the liquid crystal molecules, for example, a vertical electric field method such as a TN method or a VA method, or a transverse electric field method such as an IPS method or a wide viewing angle opening and closing (hereinafter, FFS) method is known (for example, Patent Document 1). On the other hand, in recent years, since the economics of the liquid crystal display element or the organic EL element in the production steps are also extremely important factors, the recycling of the element substrate has also been sought. In other words, in the case of forming a liquid crystal alignment film by a liquid crystal alignment agent, it is possible to easily carry out the steps of removing the liquid crystal alignment film from the substrate and recovering the substrate to be reprocessed when the defect is found in the inspection for the alignment property or the like. . However, the liquid crystal alignment film produced by the liquid crystal alignment agent of the above-mentioned conventionally proposed one is often insoluble in the organic solvent after baking, and is intended to reduce film reduction. Further, the composition of the recrystallized liquid crystal alignment agent studied so far is difficult to achieve the desired purpose even when it is used as a liquid crystal alignment agent for a lateral electric field. Therefore, it is necessary to re-evaluate the liquid crystal alignment agent. Whether or not there is excellent remanufacturability, it is necessary to re-examine whether or not the composition of the optimum composition can be achieved. [Prior Art Document] [Patent Document] [0004] [Patent Document 1] JP-A-2013-167782

[Problem to be Solved by the Invention] The present invention has an object of providing a liquid crystal alignment agent capable of producing a liquid crystal alignment film having excellent remanufacturability. [Means for Solving the Problems] [0006] The inventors of the present invention have found in order to solve the above problems, and have found that a tetracarboxylic acid containing a specific aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride has When a polyamine derivative of a specific structure of a diamine and a ruthenium imidized polymer of polyglycine are used, a liquid crystal alignment film having excellent remanufacturability can be obtained, and thus the present invention has been completed. That is, the present invention has been proposed based on the above results, and has the following main contents. A liquid crystal alignment agent comprising: a tetracarboxylic acid represented by the following formula (1) and a tetracarboxylic acid of an aliphatic tetracarboxylic dianhydride in a ratio of 10:90 to 90:10 Polymerization of at least one selected from the group consisting of a polyphthalic acid obtained by reacting a dianhydride component with a diamine component of a diamine represented by the following formula (2), and a ruthenium imidized polymer of the polyaminic acid Matter, with organic solvents. [0008] (In the formula (1), i is 0 or 1, and X is a single bond, an ether bond, a carbonyl group, an ester bond, a phenyl group, a linear alkyl group having 1 to 20 carbon atoms, or a carbon atom. a branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a sulfonyl group, a guanamine bond, or a group formed by the combination, wherein the carbon number is 1 to 20 The alkyl group can be interrupted by the bond selected by the ester bond and the ether bond. The carbon atom of the phenyl and alkyl groups can be derived from a halogen atom, a cyano group, an alkyl group, a haloalkyl group or an alkoxy group. And one or a plurality of the same or different substituents selected by the haloalkoxy group. In the formula (2), Y ₁ is: having an amine group, an imido group, and a nitrogen-containing heterocyclic ring a divalent organic group having at least one structure selected from the group, or a divalent organic group selected from an amine group, an imido group and a nitrogen-containing hetero ring substituted with a pyrolytic group on the nitrogen atom, B ₁ and B ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group which may have a substituent. [0010] 2. The liquid crystal alignment agent according to 1, wherein 10 to 100 mol% of the tetracarboxylic dianhydride component is tetracarboxylic dianhydride and aliphatic tetracarboxylic acid represented by the above formula (1). Diacid anhydride. [0011] 3. The liquid crystal alignment agent according to 1 or 2, wherein 10 to 100 mol% of the diamine component is a diamine of the formula (2). ~ (YD-5) of the selected structure of a liquid crystal alignment agent according to any of the [0012] 4. 1-3, wherein the formula Y ₁ (2) represented by the following formula in the (YD-1) At least one. [0013] In the formula (YD-1), A ₁ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, Z ₁ is a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In YD-2), W ₁ is a hydrocarbon group having 1 to 10 carbon atoms, and A ₂ is a monovalent organic group having a carbon number of 3 to 15 having a nitrogen atom-containing heterocyclic ring, or an aliphatic group having 1 to 6 carbon atoms. a disubstituted amino group substituted by a group. In the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W ₃ is a carbon number of 2 to 5. An alkyl group or a biphenyl group, Z ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally dissociable group, and a is an integer of 0 to 1. In the formula (YD-4), A ₃ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms. In the formula (YD-5), A ₄ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and W ₅ is a carbon number 2 to 5 alkylene oxide. base). [0015] 5. The liquid crystal alignment agent according to 4, wherein A ₁ , A ₂ , and A ₃ described in the formulas (YD-1), (YD-2), (YD-4), and (YD-5) And A ₄ , which are pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridyl At least one selected from the group consisting of hydrazine, benzimidazole, quinoline, and isoquinoline. [0016] The liquid crystal alignment agent according to any one of (1), wherein Y ₁ in the formula (2) is 2 having a structure of the following formula (YD-6) to (YD-21) At least one selected from the group of organic groups of the price. [0017] (In the formula (YD-17), h is an integer of 1 to 3, and in the formulas (YD-14) and (YD-21), j is an integer of 1 to 3). [0019] 7. The liquid crystal alignment agent according to 6, wherein Y ₁ in the formula (2) is a divalent organic group having a structure of the above formula (YD-14) and (YD-18). At least one selected from the group. [0020] The liquid crystal alignment agent according to any one of the above-mentioned formula (1), wherein the tetracarboxylic dianhydride represented by the formula (1) is 3,3',4,4'-biphenyltetracarboxylic acid. Diacid anhydride. The liquid crystal alignment agent according to any one of 1 to 8, wherein the aliphatic tetracarboxylic dianhydride is bicyclo[3.3.0]octane 2,4,6,8-tetracarboxylic acid 2 , 4:6, 8 dianhydride. A liquid crystal alignment film obtained by coating and sintering the liquid crystal alignment agent according to any one of 1 to 9. [0023] A liquid crystal display device comprising the liquid crystal alignment film of 10 described. [Effects of the Invention] The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has excellent remanufacturability. [Form of the Invention] The liquid crystal alignment agent of the present invention is characterized by containing a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (1) and an aliphatic tetracarboxylic dianhydride. a polyamic acid obtained from a diamine component containing a diamine represented by the following formula (2), and at least one polymer selected from the ruthenium imidized polymer of the polyaminic acid, and an organic solvent . [0026] In the formula (1), i is 0 or 1, and X is a single bond, an ether bond, a carbonyl group, an ester bond, a phenyl group, a linear alkyl group having 1 to 20 carbon atoms, and a carbon number. a branched alkyl group of 2 to 20, a cyclic alkyl group having 3 to 12 carbon atoms, a sulfonyl group, a guanamine bond or a group formed by the combination, wherein the carbon atoms are 1 to 20 The alkyl group may be interrupted by a bond selected by an ester bond and an ether bond, and the carbon atom of the phenyl and alkyl groups may be derived from a halogen atom, a cyano group, an alkyl group, a haloalkyl group or an alkoxy group. And one or a plurality of the same or different substituents selected by the haloalkoxy group are substituted. In the formula (2), Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, or is heated by a nitrogen atom. a divalent organic group selected from the amine group, the imine group and the nitrogen-containing heterocyclic ring substituted by the dissociable group, and B ₁ and B ₂ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent Base, alkenyl, alkynyl. Hereinafter, each component will be described in detail. <Tetracarboxylic acid dianhydride component> The tetracarboxylic dianhydride represented by the above formula (1) is, for example, the compounds listed below, but is not limited thereto. [0029] (wherein q represents an integer from 1 to 20). [0031] The tetracarboxylic dianhydride represented by the formula (1) has a highly enhanced remanufacturability effect, and i in the formula (1) is a tetracarboxylic dianhydride of 1, that is, has two The above benzene ring tetracarboxylic dianhydride is preferred, and in the above specific examples, (1-2) to (1-11) are preferred, and both the biphenyl structure and the rigid structure are included, and The 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by 1-5) is particularly preferred. The specific aliphatic tetracarboxylic dianhydride used in the present invention is, for example, a tetracarboxylic dianhydride represented by the following formula (3). [0033] In the formula, X ₁ may be any one of the following (X-1) to (X-28). [0035] [0036] [0037] In the formula (X-1), R ₃ to R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and a hydrogen atom or a methyl group is preferred. [0039] Among the above, (X-1) to (X-20) are preferred from the viewpoint of not containing an aromatic moiety, and (X-10) is particularly difficult from the viewpoint of being less susceptible to thermal imidization. good. The total amount of the tetracarboxylic dianhydride and the aliphatic acid dianhydride represented by the formula (1) of the present invention is the same as the total amount of the tetracarboxylic dianhydride component used in the production of the component (A). When the amount is too small, the effects of the present invention will not be obtained. Therefore, the total amount of the tetracarboxylic dianhydride and the aliphatic acid dianhydride represented by the formula (1) is preferably 10 to 100 mol%, more preferably 50, based on 1 mol of the total tetracarboxylic dianhydride. ~100% by mole, especially preferably 80 to 100% by mole. The content ratio of the tetracarboxylic dianhydride to the aliphatic acid dianhydride represented by the formula (1) is from 10:90 to 90:10, but preferably from 20:80 to 80:20, more preferably 40. The ratio of 60 to 60:40, particularly preferably from 46:54 to 54:46, is substantially optimal in terms of equivalents. The tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride represented by the formula (1) may be used singly or in combination of plural kinds, in which case represented by the formula (1) The total amount of the tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride is preferably the same as the above preferred amount. The polyphthalic acid contained in the liquid crystal alignment agent of the present invention may be, in addition to the tetracarboxylic dianhydride represented by the formula (1) and the aliphatic tetracarboxylic dianhydride, the following formula (4). Represented by tetracarboxylic dianhydride. [0044] In the formula (4), X is a tetravalent organic group, and the structure thereof is not particularly limited. In the case of a specific example, for example, the structures of the following formulae (X-31) to (X-36) and the like. [0046] <Diamine component> The diamine component used in the production of the liquid crystal alignment agent of the present invention is a diamine containing the above formula (2). In the formula (2), Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, or is heated by a nitrogen atom. a divalent organic group selected from the amine group, the imine group and the nitrogen-containing heterocyclic ring substituted by the dissociable group, and B ₁ and B ₂ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent Base, alkenyl, alkynyl. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group and the like. The alkenyl group, for example, one or more CH-CH structures present in the above alkyl group are substituted by a C=C structure, more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, or an iso- Propylene group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like. An alkynyl group, for example, one or more CH ₂ -CH ₂ structures present in the aforementioned alkyl group are substituted by a C≡C structure, more specifically, for example, an ethynyl group, a 1-propynyl group, a 2-propene group Alkynyl and the like. When the alkyl group, the alkenyl group, and the alkynyl group have a carbon number of 1 to 10 as a whole, they may have a substituent, and may further form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent is bonded to a part of the parent skeleton to form a ring structure. Examples of the substituent, for example, a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate ester Alkyl, amidino, alkyl, alkenyl, alkynyl and the like. The halogen group as a substituent is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. The aryl group as a substituent is, for example, a phenyl group or the like. The aryl group may be further substituted with the other substituents described above. The organooxy group as a substituent has, for example, a structure represented by OR. The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like. The organothio group as a substituent has, for example, a structure represented by -SR. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the alkylthio group are, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group and the like. The organoalkylene group as a substituent has, for example, a structure represented by -Si-(R) ₃ . The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the alkylalkyl group are, for example, trimethyldecyl, triethyldecyl, tripropyldecyl, tributyldecyl, tripentyldecyl, trihexyldecyl, pentyldimethyl a decyl group, a hexyl dimethyl decyl group, and the like. The thiol group as a substituent has, for example, a structure represented by -C(O)-R. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the mercapto group include, for example, a mercapto group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group and the like. The ester group as a substituent has, for example, a structure represented by -C(O)OR or -OC(O)-R. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. The thioester group as a substituent has, for example, a structure represented by -C(S)OR or -OC(S)-R. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. The phosphate group as a substituent has, for example, a structure represented by -OP(O)-(OR) ₂ . The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. The mercaptoamine group as a substituent, for example, has -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC (O) Structure represented by R. The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. The aryl group as a substituent is, for example, the same as the above-mentioned aryl group. The aryl group may be further substituted with the other substituents described above. The alkyl group as a substituent is, for example, the same as the alkyl group described above. The alkyl group may be further substituted with the other substituents described above. The alkenyl group as a substituent is, for example, the same as the above-mentioned alkenyl group. The alkenyl group may be further substituted with the other substituents described above. The alkynyl group as a substituent is, for example, the same as the alkynyl group described above. The alkynyl group may be further substituted with the aforementioned other substituents. In general, when a large structure is introduced, the reactivity of the amine group or the liquid crystal alignment property can be lowered, so B ₁ and B ₂ , for example, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent The base is preferably a hydrogen atom, a methyl group or an ethyl group. The structure of Y ₁ in the formula (2), for example, may have at least one selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, but only a nitrogen atom When at least one structure selected from the group consisting of an amine group, an imine group and a nitrogen-containing hetero ring substituted by a pyrolytic group is used, the structure thereof is not particularly limited. Therefore, the specific example includes at least one selected from the group consisting of an amine group represented by the following formulas (YD-1) to (YD-5), an imine group, and a nitrogen-containing heterocyclic ring. A divalent organic group of the structure of the species. [0067] In the formula (YD-1), A ₁ is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms, Z ₁ is a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In the formula (YD-2), W ₁ is a hydrocarbon group having 1 to 10 carbon atoms, and A ₂ is an organic group having a monovalent number of carbon atoms of 3 to 15 having a nitrogen atom-containing heterocyclic ring, or a carbon number of 1 to 6. A disubstituted amine group substituted with an aliphatic group. In the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W ₃ is an alkylene group having 2 to 5 carbon atoms or a stretched biphenyl group. Z ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring or a thermally dissociable group, and a is an integer of 0 to 1. In the formula (YD-4), A ₃ is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms. In the formula (YD-5), A ₄ is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms, and W ₅ is a C 2 to 5 alkyl group. The nitrogen of the formula (YD-1), (YD-2), (YD-4), and (YD-5) A ₁ , A ₂ , A ₃ , and A _{4 having} a carbon number of 3 to 15 The hetero ring of the atom is not particularly limited as long as it is a known structure. Among them, for example, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridyl And hydrazine, benzimidazole, quinoline, isoquinoline, oxazole, etc., and piperazine, piperidine, hydrazine, benzimidazole, imidazole, oxazole, and pyridine are preferred. Further, the thermally dissociable group may be a substituent which may be dissociated at room temperature and which may be dissociated upon sintering of the alignment film and may be substituted by a hydrogen atom. Specifically, for example, tert- Butoxycarbonyl and 9-fluorenylmethoxycarbonyl and the like. Further, a specific example of Y ₂ in the formula (2), for example, a divalent organic group of a nitrogen atom represented by the following formulas (YD-6) to (YD-52) can suppress the cause The viewpoint of charge accumulation by AC driving is preferably (YD-14) to (YD-21), and (YD-14) and (YD-18) are particularly preferable. [0072] In the formulae (YD-14) and (YD-21), j is an integer of 0 to 3. [0074] In the formulae (YD-24), (YD-25), (YD-28), and (YD-29), j is an integer of 0 to 3. In the formula (YD-17), h is an integer of 1 to 3. [0076] [0077] [0078] [0079] [0079] (In the formula (YD-50), m and n are each an integer of 1 to 11, and m+n is an integer of 2 to 12). The ratio of the diamine represented by the formula (2) in the polyamiled acid of the poly-proline and the polyaminic acid of the present invention is 10 to 100 moles relative to the total diamine 1 mole. The ear% is preferably more preferably 30 to 100 mol%, and particularly preferably 50 to 100 mol%. [0082] The diamine represented by the formula (2) in the polyaminic acid of the component (A) of the present invention and the ruthenium imidized polymer of the polyaminic acid may be used singly or in combination of plural kinds. Alternatively, in this case, the total amount of the diamine represented by the formula (2) is preferably in the above preferred amount. In addition to the diamine represented by the above formula (2), the polyamine contained in the liquid crystal alignment agent of the present invention may be a diamine represented by the following formula (5). Y ₂ in the following formula (5) is a divalent organic group, and the structure thereof is not particularly limited, and two or more types may be used in combination. Moreover, the specific examples thereof include the following (Y-1) to (Y-49) and (Y-57) to (Y-97). [0084] [0085] [0086] [0087] [0088] [0089] [0090] [0091] [0092] [0093] [0094] [0095] When the ratio of the diamine represented by the formula (5) is too large, the polyamino acid of the component (A) and the ruthenium imidized polymer of the polyaminic acid contained in the liquid crystal alignment agent of the present invention may There is a possibility of impairing the effect of the present invention, which is not preferable. Therefore, the ratio of the diamine represented by the formula (5) is preferably 0 to 90 mol%, more preferably 0 to 50 mol%, and particularly preferably 0 to 20 mol% based on the total diamine 1 mol. ear%. <Method for Producing Polylysine> The polylysine of the polyimide precursor used in the present invention can be synthesized by the method shown below. Specifically, the tetracarboxylic dianhydride and the diamine are used in the presence of an organic solvent at -20 to 150 ° C, preferably 0 to 70 ° C, for 30 minutes to 24 hours, preferably It is synthesized by reaction for 1 to 12 hours. The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butane from the viewpoints of solubility of the monomer and the polymer. Ester or the like is preferable, and one type may be used alone or two or more types may be used in combination. The concentration of the polymer is preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass, from the viewpoint of easily preventing precipitation of the polymer and easily obtaining a high molecular weight body. The polylysine obtained by the above method can be recovered by precipitating the polymer when the reaction solution is thoroughly stirred and injected into a poor solvent. Further, the precipitated product is precipitated several times, washed with a poor solvent, and dried at room temperature or under heating to obtain a purified polyamidonic acid powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, cellosolve, acetone, toluene, water, methanol, ethanol, and 2- Propanol and the like are preferred. <Method for Producing Polyimine] The polyimine used in the present invention can be obtained by subjecting the polyamic acid to a ruthenium reaction. In the case of producing a polyimine from a polylysine, a chemical ruthenium reaction of a catalyst is added to a solution of the polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride. For the convenience of the method. The chemical hydrazine imidization can carry out the oxime imidization reaction at a relatively low temperature, and it is preferable that the molecular weight of the polymer is not lowered in the hydrazine imidization process. The chemical hydrazine imidization is carried out by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it maintains an appropriate basicity during the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, it is preferred to carry out purification after completion of the reaction. The temperature at which the hydrazine imidization reaction is carried out can be carried out at a temperature of from -20 to 140 ° C, preferably from 0 to 100 ° C, for a reaction time of from 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the polyamido acid group, and the amount of the acid anhydride is 1 to 50 moles of the polyamido acid group, preferably 3 to 30 moles. The ruthenium imidation ratio of the obtained polymer can be controlled in such a manner that the amount of the catalyst, the temperature, and the reaction time can be adjusted. In the solution after the imidization reaction of the poly-proline, the added catalyst or the like is left in the solution, and the obtained ruthenium-based polymer is recovered and redissolved by the means described below. In the organic solvent, it is preferred as the liquid crystal alignment agent of the present invention. [0106] The polyimine solution obtained in the above manner is poured into a poor solvent with sufficient stirring to precipitate a polymer. The precipitated product is precipitated several times, washed with a poor solvent, and dried at normal temperature or under heating to obtain a purified polymer powder. The poor solvent is not particularly limited, and examples thereof include methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, and ethanol. Toluene, benzene, etc., preferably methanol, ethanol, 2-propanol, acetone, and the like. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent used in the present invention is in the form of a solution having a polymer component dissolved in an organic solvent. The molecular weight of the polymer preferably has a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 300,000, particularly preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, particularly preferably from 5,000 to 50,000. The concentration of the polymer of the liquid crystal alignment agent used in the present invention can be appropriately changed in accordance with the thickness setting of the coating film to be formed, and a uniform and defect-free coating film is formed, and 1% by mass or more is used. Preferably, the solution is stable in terms of stability, and it is preferably 10% by mass or less. A particularly preferred polymer concentration is from 2 to 8% by mass. The organic solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as the polymer component can be uniformly dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidine. Ketone, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, Γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even a solvent which cannot uniformly dissolve the polymer component alone may be used in combination with the above organic solvent as long as it does not precipitate a polymer. In addition to the above-mentioned solvent, the organic solvent contained in the liquid crystal alignment agent can be generally used in combination with a solvent which can improve the coating property or improve the surface smoothness of the coating film when the liquid crystal alignment agent is applied. In the liquid crystal alignment agent of the present invention, these mixed solvents are also suitably used. Specific examples of the organic solvent which can be used in combination are, for example, the following, but are not limited to the examples. For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2- Pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexyl Alcohol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1, 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, dipropyl ether, dibutyl ether, Dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2- Heptone, 4-heptanone, 2,6-dimethyl-4-heptanone 4,6-Dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, decyl alcohol, diethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate Ester, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, B Ethyl ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropane Acid methyl ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, a solvent represented by the following formulas [D-1] to [D-3], and the like. [0113] In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3] D ³ represents an alkyl group having 1 to 4 carbon atoms. Wherein a combination of preferred solvents, for example, N-methyl-2-pyrrolidone and γ-butyrolactone with ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyl Lactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl- 2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-A 2-pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and 2,6- Dimethyl-4-heptanol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether. The type and content of the solvent can be appropriately selected in accordance with a coating device for a liquid crystal alignment agent, a coating condition, a coating environment, and the like. Further, in the liquid crystal alignment agent of the present invention, the following additives may be added from the viewpoint of improving the mechanical strength of the film. [0117] [0118] The additives are preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the effect cannot be expected. When the amount is more than 30 parts by mass, the liquid crystal alignment property is lowered, and it is more preferably 0.5 to 20 parts by mass. In addition to the above, in addition to the above, the liquid crystal alignment agent of the present invention may be added with a polymer other than the polymer to change the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film. a dielectric material or a conductive material, a decane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinking compound for the purpose of improving the film hardness or density when the liquid crystal alignment film is used, or an improvement When the coating film is sintered, the polyaminic acid can be efficiently subjected to a ruthenium imidization reaction or the like. <Liquid Crystal Alignment Film><Method for Producing Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and sintering the film. The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used. From the viewpoint of simplification, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. Further, when the reflective liquid crystal display element is only a single-sided substrate, an opaque substance such as a germanium wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode. The method of applying the liquid crystal alignment agent of the present invention is, for example, a spin coating method, a printing method, an inkjet method, or the like. The drying and sintering steps after applying the liquid crystal alignment agent of the present invention may be selected to any temperature and time. Usually, when the organic solvent contained is sufficiently removed, it may be dried at 50 ° C to 120 ° C for 1 minute to 10 minutes, and then sintered at 150 ° C to 300 ° C for 5 minutes to 120 minutes. The thickness of the coating film after sintering is not particularly limited. However, when it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is usually 5 to 300 nm, preferably 10 to 200 nm. A method of performing alignment treatment on the obtained liquid crystal alignment film, for example, a rubbing method, a photoalignment treatment method, or the like. The rubbing treatment can be carried out using an existing friction device. At this time, the material of the rubbing cloth, for example, cotton products, nylon, enamel, and the like. The conditions of the rubbing treatment are generally in the range of 300 to 2000 rpm, a conveying speed of 5 to 100 mm/s, and a pressing amount of 0.1 to 1.0 mm. Subsequently, the residue generated by the friction cleaning by ultrasonic cleaning is removed using pure water or alcohol. [0124] A specific example of the photo-alignment processing method, for example, a method of irradiating the surface of the coating film with radiation directed in a specific direction, and depending on the case, heat treatment at a temperature of 150 to 250 ° C to impart a liquid crystal alignment ability Wait. For the radiation, for example, ultraviolet rays having a wavelength of 100 nm to 800 nm and visible rays can be used. Among them, ultraviolet rays having a wavelength of from 100 nm to 400 nm are preferred, and those having a wavelength of from 200 nm to 400 nm are particularly preferred. Further, for the purpose of improving the alignment of the liquid crystal, the coated substrate may be irradiated with radiation at a temperature of 50 to 250 °C. The exposure to radiation of 1 ~ 10,000mJ / cm ² preferably, to 100 ~ 5,000mJ / cm ² is particularly preferred. The liquid crystal alignment film obtained in the above manner can stably align liquid crystal molecules in a specific direction. Further, when the extinction ratio of the polarized ultraviolet rays is higher, it is more preferable because it can impart higher anisotropy. Specifically, the extinction ratio of the ultraviolet light which is polarized with respect to a straight line is preferably 10:1 or more, and more preferably 20:1 or more. The film irradiated with the polarized radiation obtained in the above manner may be further subjected to a contact treatment using a solvent containing at least one selected from water and an organic solvent. The solvent used for the contact treatment is not particularly limited as long as it can dissolve the solvent of the decomposition product generated by light irradiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, and butyl solution. Cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate Ester and the like. These solvents may be used in combination of two or more kinds. From the viewpoint of versatility or safety, it is preferred to use at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate. . It is particularly preferred to use water, 2-propanol, and a mixed solvent of water and 2-propanol. In the present invention, the contact treatment of the film irradiated with the polarized radiation and the solution containing the organic solvent enables the film and the liquid to be preferably and sufficiently contacted by using a wetting treatment, a spray treatment or the like. Way to proceed. Further, it is preferred to carry out the method of impregnating the film in the solution containing the organic solvent for preferably from 10 seconds to 1 hour, more preferably from 1 to 30 minutes. The contact treatment can be carried out at normal temperature or under heating, preferably at 10 to 80 ° C, more preferably between 20 and 50 ° C. In addition, if necessary, ultrasonic waves or the like can be applied to enhance contact. [0130] After the above contact treatment, the purpose of removing the organic solvent in the solution after use may be to wash (Rinse) or dry with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone. , or both at the same time. Further, when the film subjected to the contact treatment with a solvent described above is used for drying the solvent and realigning the molecular chains in the film, it may be heated to 150 ° C or higher. The temperature of the heating is, for example, preferably 150 to 300 ° C. When the temperature is higher, the molecular chain re-alignment can be promoted, but when the temperature is too high, there is a concern that the molecular chain is decomposed. Therefore, the heating temperature is preferably, for example, 180 to 250 ° C, and particularly preferably 200 to 230 ° C. [0133] When the heating time is too short, the effect of reorientation of the molecular chain may not be obtained. When the temperature is too long, the molecular chain may be decomposed. Therefore, it is preferably 10 seconds to 30 minutes. Minutes to 10 minutes are preferred. Further, the obtained liquid crystal alignment film can be easily dissolved in a reconstituted material, and is a film having excellent remanufacturability. The solvent used in the reconstitution may, for example, be a solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or propylene glycol monomethyl ether. Glycol ethers; glycolosolve acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc. Diethylene glycol, propylene glycol, butanediol, hexanediol, etc.; alcohols such as methanol, ethanol, 2-propanol, butanol; acetone, methyl ethyl ketone, cyclopentanone, cyclohexane Ketones such as ketone, 2-heptanone, γ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropane Methyl ester, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc., N,N-dimethylformamide, N,N- Amidoxis such as dimethylacetamide and N-methyl-2-pyrrolidone. The reconstituted material contains, for example, an alkaline component such as ethanolamine in the solvent, and a rust inhibitor which does not cause the alkaline damage electrode or the like. Manufacturers of such remanufactured materials are available, for example, Korea's Huiming Industry Co., Ltd., KPX Chemical, and the like. [0137] In order to heat the above-mentioned reconstituted material at room temperature or between 30 ° C and 100 ° C, the substrate with the liquid crystal alignment film is immersed therein for 1 second to 1000 seconds, preferably. After 30 seconds to 500 seconds, or after the spray material is spray-sprayed, the liquid is washed with an alcohol solvent or pure water. Further, the temperature of the reconstituted liquid at the time of remanufacturing is preferably a low temperature from the viewpoint of work efficiency, etc., and is usually room temperature to 60 ° C, more preferably room temperature to 40 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention is obtained by using the liquid crystal alignment agent of the present invention and preparing a substrate having a liquid crystal alignment film according to the method for producing a liquid crystal alignment film, and then forming a liquid crystal crystal by a known method. And use it as a liquid crystal display element. [0139] An example of a method of fabricating a liquid crystal lattice will be described by taking a liquid crystal display device having a passive element matrix structure as an example. Further, it may be a liquid crystal display element having an active matrix structure in which opening and closing elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display. [0140] First, a transparent glass substrate is prepared, and a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. The electrodes can be used, for example, as ITO electrodes or can form a pattern of desired image display. Next, an insulating film covering the common electrode and the segment electrode may be provided on each of the substrates. The insulating film is, for example, a film formed of SiO ₂ -TiO ₂ formed by a sol-gel method. Next, on the respective substrates, the liquid crystal alignment film of the present invention was formed by the above method. Next, the substrate on one side and the substrate on the other side are overlapped so that the alignment film faces face each other, and a sealant is used in the periphery. In the sealant, for the purpose of controlling the gap between the substrates, etc., a spacer is usually mixed. Further, it is preferable to disperse the spacer which controls the gap of the substrate in the inner portion where the sealant is not provided. One of the sealants is provided with an opening that can be filled with liquid crystal externally. [0143] Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant via the opening provided in the sealant. Subsequently, the opening portion is sealed with an adhesive. The injection method may be a vacuum injection method or a capillary phenomenon in the atmosphere. Subsequently, the setting of the polarizing plate is performed. Specifically, a pair of polarizing plates are attached to the surface opposite to the liquid crystal layer of the two substrates. Through the above steps, the liquid crystal display element of the present invention is obtained. In the present invention, the sealant may be cured by ultraviolet irradiation or heating, for example, using a reactive group having an epoxy group, an acryloyl group, a methacryl group, a hydroxyl group, an allyl group or an ethyl fluorenyl group. Resin. In particular, it is preferred to use a hardening resin having a reactive group having both an epoxy group and a (meth)acryl fluorenyl group. In the sealing agent of the present invention, an inorganic filler may be blended for the purpose of improving adhesion, moisture resistance, and the like. The inorganic filler to be used is not particularly limited, and specific examples thereof include spherical cerium oxide, molten cerium oxide, crystalline cerium oxide, titanium oxide, titanium black, cerium carbide, and nitriding. Bismuth, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, calcium citrate, aluminum silicate, lithium aluminum silicate, Zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably spherical cerium oxide, molten cerium oxide, crystalline cerium oxide, titanium oxide, titanium black, cerium nitride, nitrogen Boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate. The inorganic filler may be used in combination of two or more kinds. In the liquid crystal display device, since the liquid crystal alignment film is a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film of the present invention, it has excellent remanufacturability, and is suitable for use in a large-screen and high-definition liquid crystal television. Wait.

[Examples] Hereinafter, the experimental methods for investigating the composition or blending ratio of raw materials, the results thereof, and examples of typical production methods will be described in detail in the detailed description of the production method of the present invention. Further, the present invention is not limited by the embodiments. Description of the abbreviation used in the present example (organic solvent) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve (acidosolve) Acid dianhydride (A): (A) Acid dianhydride (B): the following formula (B) Acid dianhydride (C): the following formula (C) Acid dianhydride (D): the following formula (D) DA-1: the following formula ( DA-1) DA-2: the following formula (DA-2) DA-3: the following formula (DA-3) DA-4: the following formula (DA-4) DA-5: the following formula (DA- 5) [0148] The measurement of the viscosity, the measurement of the imidization ratio, the evaluation of the remanufacturability, the production of the liquid crystal lattice, and the method of evaluating the charge relaxation characteristics are described below. [Measurement of Viscosity] In the synthesis example, the viscosity of the polyglycolate and the polyaminic acid solution was measured at a temperature of 25 ° C using an E-type viscometer TV-25H (manufactured by Toki Sangyo Co., Ltd.). The sample amount was 1.1 mL and CORD-1 (1°34', R24). [Evaluation of Remanufacturability] The liquid crystal alignment agent of the present invention was applied onto an ITO substrate using a spin coater. After drying on a hot plate at 60 ° C for 1 minute and 30 seconds, the film was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. Subsequently, the obtained substrate was immersed in a reconstituted material (HM-R20) heated to 55 ° C for 300 seconds, developed, and then washed with running water for 20 seconds using ultrapure water. Subsequently, the air-jet treatment was carried out, and the liquid crystal alignment film completely disappeared and marked as ○, and the liquid crystal alignment film remained as marked ×. The results obtained are shown in Table 3 depending on the specific temperature of the reconstituted solution at 35 ° C and 55 ° C, respectively. (Comparative Polymerization Example 1) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g and (DA-4) 0.96 g were weighed, and NMP (25.7 g) was added thereto. At 23 ° C, nitrogen was fed in and stirred to dissolve. The diamine solution was stirred, and 3.00 g of acid dianhydride (C) was added, and 11.2 g of NMP was added thereto. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, 0.77 g of acid dianhydride (D) was added, and NMP 4 was further added. .4g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 50 ° C for 16 hours to obtain a polyaminic acid solution (PAA-1). The polyamic acid solution had a viscosity of 358 cps at a temperature of 25 °C. (Comparative Polymerization Example 2) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-2) 0.46 g was weighed, and NMP (22.3 g) was added thereto. At 23 ° C, nitrogen was fed in and stirred to dissolve. The diamine solution was stirred, and 2.00 g of acid dianhydride (C) was added, and 6.3 g of NMP was added thereto. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, 1.51 g of acid dianhydride (D) was added, and then NMP8 was added. .5g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 50 ° C for 16 hours to obtain a polyaminic acid solution (PAA-2). The polyamic acid solution has a viscosity of 333 cps at a temperature of 25 °C. (Comparative Polymerization Example 3) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-2) 0.46 g was weighed, and NMP (22.3 g) was added thereto. At 23 ° C, nitrogen was fed in and stirred to dissolve. The diamine solution was added with 4.5 g of acid dianhydride (A), and then added with 0.5 g of NMP, and stirred at 23 ° C under a nitrogen atmosphere for 2 hours, and then stirred at 50 ° C for 16 hours to obtain polylysine. Solution (PAA-3). The polyamic acid solution has a viscosity of 350 cps at a temperature of 25 °C. (Comparative Polymerization Example 4) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-2) 0.49 g was weighed, and NMP (22.3 g) was added thereto. At 23 ° C, nitrogen was fed in and stirred to dissolve. The diamine solution was stirred, and 3.00 g of acid dianhydride (C) was added, and then 12.0 g of NMP was added. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, 0.72 g of acid dianhydride (D) was added, and then NMP 4 was added. .1g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 50 ° C for 16 hours to obtain a polyaminic acid solution (PAA-4). The polyamic acid solution has a viscosity of 333 cps at a temperature of 25 °C. (Polymer Example 1) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-5) 0.78 g was weighed, and NMP 24.4 g was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 1.75 g of acid dianhydride (B) was added, and 4.3 g of NMP was added thereto. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, 1.41 g of acid dianhydride (D) was added, and then NMP8 was added. .0g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 50 ° C for 16 hours to obtain a polyamidonic acid solution (PAA-5). The polyamic acid solution has a viscosity of 240 cps at a temperature of 25 °C. (Polymerization Example 2) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g and (DA-2) 0.49 g were weighed, and NMP (22.3 g) was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 2.35 g of acid dianhydride (A) was added, and 8.3 g of NMP was added thereto. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, acid dianhydride (C) 1.80 g was added, and then NMP 10 was added. .2g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 70 ° C for 16 hours to obtain a polyaminic acid solution (PAA-6). The polyamic acid solution has a viscosity of 380 cps at a temperature of 25 °C. (Polymerization Example 3) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-3) 0.63 g was weighed, and NMP 23.4 g was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 2.35 g of acid dianhydride (A) was added, and then 8.0 g of NMP was added. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, acid dianhydride (C) 1.80 g was added, and then NMP 10 was added. .2g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 70 ° C for 16 hours to obtain a polyaminic acid solution (PAA-7). The polyamic acid solution has a viscosity of 350 cps at a temperature of 25 °C. (Polymerization Example 4) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) (2.5 g) and (DA-4) (0.95 g) were weighed, and NMP (25.7 g) was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 2.35 g of acid dianhydride (A) was added, and then 7.5 g of NMP was added. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, acid dianhydride (C) 1.80 g was added, and then NMP 10 was added. .2g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 70 ° C for 16 hours to obtain a polyaminic acid solution (PAA-8). The polyamic acid solution has a viscosity of 365 cps at a temperature of 25 °C. (Polymerization Example 5) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-5) 0.78 g was weighed, and NMP 24.4 g was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 2.35 g of acid dianhydride (A) was added, and then 7.8 g of NMP was added. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, acid dianhydride (C) 1.80 g was added, and then NMP 10 was added. .2g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 70 ° C for 16 hours to obtain a polyaminic acid solution (PAA-9). The polyamic acid solution had a viscosity of 389 cps at a temperature of 25 °C. (Polymerization Example 6) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-2) 0.49 g was weighed, and NMP 22.3 g was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 2.35 g of acid dianhydride (A) was added, and 8.3 g of NMP was added thereto. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, 1.41 g of acid dianhydride (D) was added, and then NMP8 was added. .0g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, the mixture was stirred at 70 ° C for 16 hours to obtain a polyaminic acid solution (PAA-10). The polyamic acid solution had a viscosity of 321 cps at a temperature of 25 °C. (Polymerization Example 7) A 50 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and (DA-1) 2.55 g, (DA-2) 0.49 g was weighed, and NMP (22.3 g) was added thereto. At °C, nitrogen is fed in and stirred to dissolve. The diamine solution was stirred, and 1.41 g of acid dianhydride (A) was added, and then 2.9 g of NMP was added. After stirring at 23 ° C for 2 hours under nitrogen atmosphere, 1.41 g of acid dianhydride (B) was added, and then NMP 7 was added. .9g, stirred at 23 ° C under a nitrogen atmosphere for 2 hours. Subsequently, 1.00 g of acid dianhydride (C) was added, and 5.7 g of NMP was further added thereto, and the mixture was stirred at 23 ° C for 2 hours under a nitrogen atmosphere. Subsequently, the mixture was stirred at 70 ° C for 16 hours to obtain a polyaminic acid solution (PAA-11). The polyamic acid solution has a viscosity of 365 cps at a temperature of 25 °C. (Comparative Examples 1 to 4) In a 50 mL Erlenmeyer flask in which a stirrer was placed, 15.0 g of a polyamic acid solution obtained in a comparative synthesis example was filtered, and 1.25 g of NMP and 12.25 g of BCS were added, and stirred with a magnetic stirrer. For 2 hours, the liquid crystal alignment agents (A-1) to (A-4) of Table 1 were obtained. [0164] (Examples 1 to 7) In a 50 mL Erlenmeyer flask in which a stirrer was placed, 15.0 g of a polyamidonic acid solution obtained in the synthesis example was filtered, and 1.25 g of NMP and 11.25 g of BCS were added, and stirred with a magnetic stirrer. In the hour, the liquid crystal alignment agents (B-1) to (B-7) of Table 2 were obtained. [0166] [0167] [Industrial Applicability] The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can reduce the charge accumulation due to the asymmetry of the AC drive in the liquid crystal display device of the IPS drive method or the FFS drive method. Further, the residual charge accumulated by the DC voltage can be quickly alleviated, and an IPS driving method or an FFS driving type liquid crystal display element having excellent afterimage characteristics can be obtained. Therefore, it is particularly suitable as a liquid crystal display element of an IPS driving method or an FFS driving method or a liquid crystal alignment film of a liquid crystal television.

Claims (11)

A liquid crystal alignment agent comprising: a tetracarboxylic acid dianhydride and an aliphatic tetracarboxylic dianhydride represented by the following formula (1) in a ratio of 10:90 to 90:10; a polyamic acid obtained by reacting an anhydride component with a diamine component containing a diamine represented by the following formula (2), and at least one polymer selected from the ruthenium imidized polymer of the polyaminic acid With organic solvents; (In the formula (1), i is 0 or 1, X is a single bond, an ether bond, a carbonyl group, an ester bond, a phenyl group, a linear alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms to a branched alkyl group of 20, a cyclic alkyl group having 3 to 12 carbon atoms, a sulfonyl group, a guanamine bond or a group formed by the combination, wherein the alkyl group having 1 to 20 carbon atoms , which can be interrupted by a bond selected by an ester bond and an ether bond. The carbon atom of the phenyl and alkyl groups can be derived from a halogen atom, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, and a halogen. One or a plurality of the same or different substituents selected by the alkoxy group are substituted; in the formula (2), Y ₁ is a group having an amine group, an imine group, and a nitrogen-containing heterocyclic ring. a divalent organic group selected from at least one of the structures, or a divalent organic group selected from an amine group, an imido group and a nitrogen-containing hetero ring substituted with a pyrolytic group on the nitrogen atom, B ₁ , B ₂ each independently represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group which may have a substituent. The liquid crystal alignment agent of claim 1, wherein 10 to 100 mol% of the tetracarboxylic dianhydride component is tetracarboxylic dianhydride and aliphatic acid dianhydride represented by the above formula (1). The liquid crystal alignment agent of claim 1, wherein 10 to 100 mol% of the diamine component is a diamine of the formula (2). The liquid crystal alignment agent of claim 1, wherein Y ₁ in the formula (2) is at least one selected from the structures of the following formulas (YD-1) to (YD-5); (In the formula (YD-1), A ₁ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, Z ₁ is a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; (YD-2) In the above, W ₁ is a hydrocarbon group having 1 to 10 carbon atoms, and A ₂ is a monovalent organic group having a carbon number of 3 to 15 having a nitrogen atom-containing heterocyclic ring, or is substituted with an aliphatic group having 1 to 6 carbon atoms. a disubstituted amine group; in the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W ₃ is a C 2 to 5 alkyl group. Or a biphenyl group, Z ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally dissociable group, and a is an integer of 0 to 1; in the formula (YD-4), A ₃ is carbon a heterocyclic ring containing a nitrogen atom of 3 to 15; in the formula (YD-5), A ₄ is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, and W ₅ is an alkylene group having 2 to 5 carbon atoms). The liquid crystal alignment agent of claim 4, wherein A ₁ , A ₂ , A ₃ , and A ₄ described in the formulas (YD-1), (YD-2), (YD-4), and (YD-5) , by pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridyl At least one selected from the group consisting of hydrazine, benzimidazole, quinoline, and isoquinoline. The liquid crystal alignment agent of claim 1, wherein Y ₁ in the formula (2) is selected from the group consisting of divalent organic groups having the structures of the following formulas (YD-6) to (YD-21) At least one of them; (In the formula (YD-17), h is an integer of 1 to 3, and in the formulas (YD-14) and (YD-21), j is an integer of 1 to 3). The liquid crystal alignment agent of claim 6, wherein Y ₁ in the formula (2) is selected from the group consisting of divalent organic groups having the structures of the above formulas (YD-14) and (YD-18) At least one. The liquid crystal alignment agent of claim 1, wherein the tetracarboxylic dianhydride represented by the above formula (1) is 3,3',4,4'-biphenyltetracarboxylic dianhydride. The liquid crystal alignment agent of claim 1, wherein the aliphatic tetracarboxylic dianhydride is bicyclo[3.3.0]octane 2,4,6,8-tetracarboxylic acid 2,4:6,8 dianhydride. A liquid crystal alignment film which is obtained by coating and sintering a liquid crystal alignment agent according to any one of claims 1 to 9. A liquid crystal display element comprising the liquid crystal alignment film of claim 10.