TW201132745A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent which is capable of providing a liquid crystal alignment film that is resistant to film separation or chipping during a rubbing process, has high voltage holding ratio, and does not easily accumulate electrical charges at the initial stage even when a direct current voltage is applied thereto. Specifically disclosed is a liquid crystal aligning agent that contains at least one kind of polymer selected from among polyamic acids, each of which is obtained by having a diamine component containing a diamine represented by formula (1) react with a tetracarboxylic acid dianhydride component, and polyimides that are obtained by imidizing the polyamic acids. (In the formula, Ar represents an isocyclic aromatic compound or a nitrogen atom-containing heterocyclic aromatic compound, and the hydrogen atom on a carbon atom or nitrogen atom constituting the ring may be substituted.)

Description

[Technical Field] The present invention relates to a liquid crystal alignment treatment agent for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element. [Prior Art] At present, the liquid crystal alignment film of the liquid crystal display element mainly uses a liquid crystal alignment treatment agent which is coated with a solution of a polyamidene precursor such as polyacrylamide or a soluble polyimine, and is burned. Then, a so-called polyimine-based liquid crystal alignment film which is subjected to rubbing treatment is applied. The liquid crystal alignment film not only controls the alignment state of the liquid crystal but also affects the characteristics of the liquid crystal display element. In particular, the problem of film peeling during the rubbing treatment, the problem of reduction, and the suppression of the decrease in the contrast of the liquid crystal display element with the high precision of the liquid crystal display element or the reduction of the afterimage phenomenon become important. In the polyimine-based liquid crystal alignment film, it is known to use a polyamic acid other than polyacrylic acid or a ruthenium-based group, in addition to reducing the time before the afterimage disappears due to a DC voltage. A liquid crystal alignment treatment agent of a tertiary amine having a specific structure (see, for example, Patent Document 1), and a liquid crystal alignment treatment agent containing a soluble polyimine having a specific diamine such as a pyridine skeleton as a raw material (refer to, for example, the patent document) 2) In addition, in the polyimine-based liquid crystal alignment film, as long as the voltage maintenance ratio is increased and the time before the afterimage due to the DC voltage is shortened, the polyamine or its hydrazine imidization is removed. In addition to polymers and the like, it is also known to use a compound selected from a compound containing a carboxylic acid group in a molecule and a compound having a carboxylic anhydride group of 201132745 and a compound having a tertiary amino group in the molecule. The liquid crystal alignment treatment agent (see, for example, Patent Document 3). [PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a film which can be peeled off or reduced in friction and has a high voltage holding ratio, and it is difficult to cause an initial stage even if a DC voltage is applied. A liquid crystal alignment treatment agent for a liquid crystal alignment film of charge accumulation. [Means for Solving the Problem] As a result of active research, the present inventors have found that polyamines containing a specific diamine compound containing a novel compound as a diamine component are contained, and/or the polyamic acid is subjected to ruthenium imine. The liquid crystal alignment treatment agent of the obtained polyimine is extremely effective in achieving the above object, and thus the present invention has been completed. That is, the present invention has the following object: (1) A liquid crystal alignment treatment agent containing a diamine component and a tetraresin acid of a diamine compound represented by the following formula π]: -6-201132745 At least one polymer selected from the group consisting of a polylysine obtained by reacting a dry component and a polyimine obtained by subjecting the polyamic acid to ruthenium imidization, ^-Ar

(wherein 'Ar' represents a carbocyclic aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom, and a hydrogen atom constituting a ring or a hydrogen atom of a nitrogen atom may be substituted). (2) The liquid crystal alignment treatment agent according to the above (1), wherein Ar of the formula [1] is a carbocyclic aromatic compound of a six-membered ring or a heterocyclic aromatic compound of a nitrogen-containing atom of a six-membered ring. (3) The liquid crystal alignment treatment agent according to the above (1), wherein Ar of the formula [1] is a heterocyclic aromatic compound containing a nitrogen atom of a five-membered ring. (4) The liquid crystal alignment treatment agent according to the above (1), wherein Ar of the formula [1] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine. (5) The liquid crystal alignment treatment agent according to the above (1), wherein A r of the formula [i] is a azole, an oxadiazole, a thiazole, a thiadiazole, a pyrrole, an imidazole, a pyrazole or a triazole. (6) The liquid crystal alignment treatment agent according to the above (1), wherein the diamine compound represented by the formula [1] is a compound represented by the following general formula [4] to formula [6] (anthraquinone and The above synonymous)' 201132745 [Chemical 2]

(7) The liquid crystal alignment treatment agent according to the formula (1), wherein the compound represented by the formula [1] is a compound represented by the following formula [2] (Ar system and the above Synonymous).

H2N

(8) The liquid crystal alignment agent according to any one of the above-mentioned items, wherein the diamine compound represented by the following formula [3] is contained at least 1 mol% or more Diamine component: H2N-A r ' ~Ri_Nh-R2 [3] (wherein Ar' represents a phenyl or anthracene group, and 1 represents an alkylene group having a carbon number of 1 to 5 'R2 represents a carbon number of 1 to 5 Alkyl). The liquid crystal alignment treatment agent according to any one of the above aspects, wherein the tetracarboxylic dianhydride component comprises a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure. (10) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of the above (1) to (9) to a substrate to which an electrode is attached, and firing the substrate. -8 - 201132745 (11) A liquid crystal display member comprising the liquid crystal alignment film according to (10) above. (12) A diamine compound represented by the following formula [1], ^Ar

(In the formula, Ar represents a carbocyclic aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom, and a hydrogen atom constituting a carbon atom of a ring or a nitrogen atom may be substituted). (13) The diamine compound according to the above (12), wherein Ar of the formula π] is a carbocyclic aromatic compound of a six-membered ring or a heterocyclic aromatic compound containing a nitrogen atom of a six-membered ring. (14) The diamine compound according to the above (12), wherein Ar of the formula [j] is a heterocyclic aromatic compound having a nitrogen atom of a five-membered ring. (1) The diamine compound according to (1) above, wherein Ar of the formula [i] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine. (16) A diamine compound according to the above (12), wherein Ar is an oxazole, an oxadiazole, a thiazole, a thiadiazole, a pyrrole, an imidazole, a pyrazole or a triazole. (1) The diamine compound of the above formula (1), wherein the diamine compound represented by the formula [1] is a compound represented by the following formula [4] to formula [6], 201132745 [Chemical 5]

[4]

H2N

The arsenic compound of the above formula (1 2), wherein the compound is a compound represented by the following formula [2]:

H2N

(19) ''Polymeric acid or polyimine, which is a diamine component and tetradecanoic acid containing the diamine compound according to any one of the above (1 2) to (1 8) a polyaminic acid obtained by the reaction of the component 1 or a polyimine obtained by subjecting the polyamic acid to ruthenium imidation. [Inventive effect] The liquid crystal alignment treatment agent of the invention can obtain film peeling during rubbing or A liquid crystal alignment film having a high voltage holding ratio and having a high DC voltage is hard to cause initial charge accumulation even when a DC voltage is applied to the liquid crystal cell, and a liquid crystal panel having excellent characteristics can be produced by using a liquid crystal alignment film. Further, according to the present invention, there is provided a novel diamine compound which can be used as a raw material of polyamic acid and polyimine which is a liquid crystal alignment agent. [Embodiment] -10-201132745 The liquid crystal compounding agent of the present invention is a polyamic acid obtained by reacting a diamine component containing a specific diamine compound represented by the following formula [1] with a tetracarboxylic dianhydride component. And a liquid crystal compounding agent for at least one polymer of the polyamine which is obtained by hydrazine imidation of the polyamic acid. The specific diamine compound contains a novel compound not described in the literature, and by using the specific diamine compound, even if the rubbing treatment is necessary in the liquid crystal alignment treatment, the film peeling or reduction at the time of rubbing can be reduced, and the obtained liquid crystal alignment film can be obtained. The voltage holding ratio is high, that is, even if a DC voltage is applied to the liquid crystal cell, it is difficult to cause accumulation of initial charges. <Diamine compound of the formula [1]> In the above formula [1], Ar represents a carbocyclic aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom, and since this Ar is a site related to the charge and reception, It is preferably an electrically active structure in which a heterocyclic aromatic compound containing a nitrogen atom is preferred.

Ar is not particularly limited as long as it is a carbocyclic aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom. However, when a structure having a large volume or a ring having a large molecular weight is introduced, there is a possibility that liquid crystal alignment property is disturbed. The lower molecular weight. In addition, since Ar is a base of valence, in the present specification, as described above, it is described as a carbocyclic aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom, etc. 'But Ar constitutes a monovalent value. a base, so if it is strictly expressed in the case of a carbocyclic aromatic compound, it means that a residue of a hydrogen atom is removed from a carbocyclic aromatic compound, and when it is a compound containing a nitrogen atom, a heterocyclic aromatic-11 - 201132745 compound It means the removal of a residue of a hydrogen atom from a heterocyclic aromatic compound containing a nitrogen atom. Ar is also the same as benzene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazole, oxadiazole, thiazole, thiadiazole, pyrrole, imidazole, pyrazole or triazole, meaning from such compounds Remove each residue of a hydrogen atom. The form of the ring of the carbocyclic aromatic compound of Ar or the heterocyclic aromatic compound containing a nitrogen atom in the above formula [1] is not particularly limited, and good properties can be obtained for the five-membered ring and the six-membered ring. The carbon ring aromatic compound of the five-membered ring or the heterocyclic aromatic compound containing a nitrogen atom is known to have higher reactivity than the ring itself of the six-membered ring. Therefore, in the firing process at a high temperature which is performed at the time of formation of the liquid crystal alignment film, the ring reacts to cause crosslinking, which is preferable from the viewpoint of friction resistance. On the other hand, in terms of electrical characteristics of the liquid crystal alignment film, a carbon ring aromatic compound having a six-membered ring having a high stability or a heterocyclic aromatic compound containing a nitrogen atom is preferred. Further, Ar in the formula [1] may be obtained by linking the same ring such as biphenyl or bipyridine, or may be formed by linking different kinds of rings such as phenylpyridine or phenylthiophene. It may also be a condensed ring structure such as quinoline or benzimidazole. Specific examples of the above carbocyclic aromatic compound are cyclopentadiene, benzene, anthracene, naphthalene, anthracene, phenanthrene, pyrene, naphthacene, benzoxylene, and perylene. , pentacene, Phenalene, hydrazine, hydrazine, biphenyl, etc. -12- 201132745 Further, specific examples of the above heterocyclic aromatic compound containing a nitrogen atom are exemplified as pyrrole, pyridine, pyridazine , pyrimidine, pyrazine, triazine, tetrazine, imidazole, pyrazole, oxazole, isoxazole, oxadiazole, thiazole, isothiazole, thiadiazole, triazole, tetrazole, hydrazine, carbazole, benzene Imidazole, benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, salivary, isoquinoline, porphyrin, Phthalazine, porphyrin, hydrazine, naphthalene Naphthyridine), Pteridine, hip hop, coumarin, isocoumarin, miso, Phenanthroline, thienopyridine, 咲 并 and D ratio steep ( Furopyridines), D introduces indolizine, quinoline D, and carbolin. Further, the N - oxime moiety in the pyrrole, pyrazole, imidazole or the like may be alkylated as such or may be methylated or the like.

Preferred specific examples of Ar are exemplified by cyclopentadiene, benzene, anthracene, naphthalene, anthracene, anthracene, biphenyl, pyrrole, pyridine, pyridazine, pyrimidine, pyrazine 'triazine, tetrazine, imidazole, pyrazole, and evil. Azole, isoxazole, oxadiazole, thiazole, isothiazole, thiadiazole, triazole, tetrazole, guanidine, oxazole, benzimidazole, benzoxazole 'benzisoxazole, benzothiazole, Benzoisothiazole, quinoline, isoquinoline, porphyrin, pyridazine, quinazoline, anthraquinone, naphthyridine, acridine, hydrazine, coumarin, isocoumarin, carbazole, thienopyridine, furan And pyridine, xiaoxiao, porphyrin pyridine, porphyrin. Most preferred are benzene, pyridine, pyridazine, pyrimidine, pyridinium, triazine, pyroline, oxazole, oxadiazole, thiazole, thiadiazole, imidazole, oxime or triazole. The carbon atom or the hydrogen atom on the nitrogen ring constituting the above-mentioned carbocyclic aromatic compound or heterocyclic aromatic compound containing a nitrogen atom may also be substituted. -13- 201132745 There are no particular restrictions on the type and number of substituents, but electron-donating substitutions such as methyl, ethyl, alkoxy, methoxy, ethoxy, amine, and dimethylamino groups are relatively small. The electron-donating substituent having a small molecular weight such as a carboxyl group, a nitro group or a cyano group is preferred because it permits the activation of electrons. The position of the substituent with the carbocyclic aromatic compound or the heterocyclic aromatic compound is not particularly limited. However, in the case of the nitrogen-containing heterocyclic aromatic compound, the position of the substituent is preferably a position not adjacent to the nitrogen atom. On the other hand, from the viewpoint of liquid crystal alignment property or friction resistance when liquid crystal alignment film is formed, or difficulty in synthesis, etc., it is preferably a carbon ring which is unsubstituted or substituted with a smaller substituent such as a methyl group or an ethyl group. An aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom. In the diamine represented by the formula [1], the position of each substituent on the benzene ring is not particularly limited. From the viewpoint of liquid crystal alignment in the case of a liquid crystal alignment film, the positional relationship between the two amine groups is preferably a meta or para position, and the viewpoint of improving the solvent solubility of polyperuric acid or polyimine. Words are better for the position. When the positional relationship between the two amine groups is meta, that is, when the 1,3 -diaminobenzene structure is constructed, the position of the methyl ester is preferably 4 or 5, especially to improve the nucleophilicity of the acetaminophen. The effect is preferably 5 in terms of the effect or the ease of synthesis. A preferred specific example of the diamine represented by the general formula [1] is a compound of the following formula [2], formula [4], formula [5] or formula [6]. -14 - 201132745 [Chem. 7]

Further, in the formula, 'A r is preferably benzene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, pyrrole 'oxazole, oxadiazole, thiazole, thiadiazole, imidazole 'pyrazole or triazole. <Synthesis of the diamine compound of the formula [1]> The synthesis method of the diamine represented by the general formula [1] is not particularly limited, and for example, a dinitro compound represented by the following formula [7] can be synthesized, and The method synthesizes a method in which a nitro group is converted into an amine group. [化8] η

The dinitro compound represented by the above formula [7] can be synthesized by esterification of the corresponding dinitrobenzyl alcohol as described below. Namely, it is synthesized by reacting dinitrobenzyl alcohol with carboxyphosphonium chloride or acid dianhydride in the presence of a base such as pyridine or triethylamine. Further, the Ar system corresponds to Ar in the amine of the above-mentioned general formula [丨] -15-201132745 which is the object of interest. The 3,5-di-X 'dinitrobenzyl alcohol is exemplified by 2,4-dinitrobenzyl alcohol, nitrohexyl alcohol, 2,5-dinitrobenzyl alcohol and the like. [化9] Ο ο 〇&lt;fH N〇2 or Ο

Alkali, solvent ^Ar &gt; 〇2N~Cf $ &amp; The above formula [7] represents the reduction of the dinitro compound, and the method of the diamine represented by the formula [1] is not particularly limited, and may be carried out by &lt; Carbon, platinum oxide, Raney nickel, lead black, lanthanum-alumina, white carbon, etc. as a catalyst, in a solvent such as ethyl acetate, toluene, tetrahydrofuran, or alcohol, with hydrogen, hydrazine, hydrogen chloride (Diamine component) The diamine represented by the above formula [1] can be obtained as a polyamine derivative with a tetracarboxylic dianhydride. In the present invention, the diamine used in the synthesis of polyamic acid may be only a diamine represented by the formula [1], or one or more of the other diamines may be combined. As for the diamine component, the solubility of the imine in an organic solvent can be obtained by containing the polypyridic acid obtained by the formula [1] and the imidization of the polyamine. Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent containing the polyamidoximine has a high frictional value and a high voltage holding ratio, and even if a direct current voltage is applied to the liquid crystal cell, it is obtained by using palladium- or dioxane sulfide. . The amine obtained by the reaction is selected as the amine, and the polypyruic acid or the poly-resistance is also difficult. -16-201132745 causes initial charge accumulation. In order to obtain such characteristics, the diamine represented by the formula [1] is preferably a total of 5 to 1% by mole of the diamine component used in the synthesis of the polyamic acid, more preferably 1 0 to 8 0 Ear %, preferably 2 0~5 0 mol%. Among the above diamine components, the diamine used in combination with the diamine represented by the formula [1] is not particularly limited. Specific examples of such diamines are shown below. Examples of alicyclic diamines are 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-di Amino-3,3'-dimethyldicyclohexylamine, isophoronediamine, and the like. Examples of aromatic diamines are o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diamine. Toluene, 3,5-diamino43-diallylaniline, 2,4-diamino-1,1^-diallylaniline, 1,4-diamino-2-methoxy Benzobenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5 -dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-di Aminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl Diphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'.diamine Diphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'- Diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-amino group) Phenoxy)benzene, 3,5-bis(4-aminophenoxy) Benzoic acid, 4,4'-bis(4-aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-( 4-aminophenoxy)phenyl]hexafluoropropane, -17- 201132745 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-amino) Phenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-double (4-Aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane , 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diamino Naphthalene, 1,5-diaminonaphthalene, 1,5-diaminostilbene, 1,3-diamine-xylene, 1,6-diaminopyrene, 1,8-diamine Diphthalaphthalene, 2,7-diaminoguanidine, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine 1, 2 - bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis ( 4-aminophenyl)pentane, 1,6-bis(4-amine Phenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl) ) decane, 1,1 〇 bis(4-aminophenyl) decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) Butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxyl) Heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminobenzene Oxy) decane, bis(4-aminophenyl)propane-1,3-dicarboxylate, bis(4-aminophenyl)butane-1,4-dicarboxylate, di(4-amino) Phenyl)penta-1,5-diester, bis(4-aminophenyl)hex-1,6-dicarboxylate, bis(4-aminophenyl)heptane-1,7-dicarboxylate 'Bis(4-aminophenyl)octane-1,8-diester, bis(4-aminophenyl)phosphonium-1,9-dicarboxylate, bis(4-aminophenyl)fluorene- 1,10-diester, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis-18- 201132745 [4-(4-aminophenoxy) Phenoxy]butane, 1,5-bis[4- ( 4- Phenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminobenzene) Oxy)phenoxy]heptane, 1,8-bis[4·(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4.aminophenoxy) Phenoxy]decane, 1,1 fluorene-bis[4-(4-aminophenoxy)phenoxy]nonane, and the like. Examples of heterocyclic diamines are 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diamine. Dibenzofuran, 3,6-diaminocarbazol, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminobenzene Base)-1,3,4-oxadiazole and the like. Examples of aliphatic diamines are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6 -diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, U9-diaminodecane, 1,10-diaminodecane, 1,3-di Amino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1, 7-Diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12- Diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like. Examples of the aromatic-aliphatic diamine are exemplified by the diamine represented by the formula [3]. Η 2 N — A r ' - R 1 — N Η — R 2 [3] wherein Ar' represents a phenyl or anthranyl group 'I represents a carbon number of 1 to 5, preferably 1 to 3 In the hospital base, R2 represents a hydrogen atom or a courtyard group having a carbon number of 1 to 5, preferably a hydrogen atom or a methyl group. Specific examples of the diamine represented by the formula [3] are exemplified by 3-aminobenzylamine, 4--19-201132745 aminobenzylamine '3-amino-N-methylbenzylamine, 4·amine --N-methylbenzylamine, 3-aminophenethylamine, 4·aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methyl Phenylethylamine, 3-(3.Aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylamine Propyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylamine Benzyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylamino) Amyl) aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-( 6-Aminonaphthyl)ethylamine and the like. When the diamine and the diamine oxime represented by the formula [1] are represented by the formula [3], the solubility of the obtained polyglycolic acid or polyimine (hereinafter referred to as a polymer) in an organic solvent is further improved. Further, it is preferable because it is excellent in liquid crystal alignment when used as a liquid crystal alignment film. Further, when the diamine (hereinafter also referred to as a tilted diamine) which increases the pretilt angle of the liquid crystal described later is used, the effect of further increasing the liquid crystal pretilt angle can be attained. Therefore, when a pretilt angle of the same size is to be obtained, a large inclination angle can be obtained even if the amount of the tilted diamine used is small. Further, improvement in printability of the liquid crystal alignment treatment agent can be expected. The preferred content of the diamine represented by the formula [3] is 10 to 80 mol%, preferably 20 to 70 mol%, based on the total amount of the diamine component. As for the diamine (also referred to as a tilted diamine) which can increase the pretilt angle of the liquid crystal, it can be exemplified by having a long chain building group, a perfluoro yard group, an aromatic cyclic group, an aliphatic cyclic group, or a combination thereof. a diamine such as a steroid skeleton or the like. -20- 201132745 These diamines can be used together with the diamines represented by the formula [1]. Specific examples of the inclined diamine are listed below, but the present invention is not limited to these. Further, in the following formulas [12] to [38], j represents an integer of 5 to 20, and k represents an integer of 1 to 20. [Chemical 10] NH h2n-^^- 0(CH2)jCH3 [12]

H2N nh2 h2n-hQ&gt; NH2 0~O~O_(cH2)kCH3 [14] nh2 0_O~O~〇(CH2)kCH3 [13]

H2N

(CH2)kCH3 [15] -21 - 201132745 [化11] nh2 H2N-^^ [16] 0(CH2)kCH3 〇 H2

n/Cv^v〇(CH2)kCH3 V [171 NH2 0(CH2)kCH3

[化 12] nh2

H2N

[19]

-22- 201132745 [Chem. 13]

(CH2)kCH3 [22] (CHACHs [23]

[2 sentences [化14]

[30]

Nh2 cH NH2 ~QrQrw (CH2)kCH3 [31] -23- 201132745 [Chem. 15]

[34] (Cri^CHa

[Chemistry 16]

Among the diamines of the above formulas [12] to [38], the diamine of the formula [12] is preferred because it is excellent in liquid crystal alignment. The diamine of the formula [1 9 ]~[2 6 ] can be preferably used in 〇CB ( Optically -24- 201132745) because of the extremely high pretilt angle.

Compensated Bend 'optical compensation bending' alignment film for liquid crystal (alignment film for 〇cB), alignment film for vertical alignment mode liquid crystal (alignment film for VA)° For example, for alignment film of TN liquid crystal (pretilt angle 3 to 5), The diamine content of the formula [1 2 ] is preferably from 10 to 30 mol% of the total diamine component, in the alignment film for OCB or the alignment film for VA (pretilt angle: 1 to 90), and the formula [19] The diamine content of [26] is preferably from 5 to 40 mol% of the total diamine component. In consideration of the balance of various properties such as solubility of polyphthalic acid or polyimine used in the liquid crystal alignment agent of the present invention, alignment property of liquid crystal, tilt angle, voltage maintenance ratio, and accumulated electric charge, for example, the formula [1] is used. In the case of the diamine component represented by the formula [3] and the formula [12], the preferred ratio of each diamine component is preferably from 10 to 50% by mol [Equation [1]) / 20 to 80% (formula) [3] ) /10~30% (form [12]), more preferably 20~40% (form [1]) / 30~50% (form [3]) /10~30% (form [12] ). <Tetracarboxylic acid dianhydride component> The polycarboxylic acid or polyimine which is required for the liquid crystal alignment treatment agent of the present invention, the tetracarboxylic dianhydride component which is reacted with the above diamine component is not particularly limited. Namely, it may be a tetracarboxylic dianhydride or two or more kinds of tetracarboxylic dianhydrides. In the liquid crystal alignment treatment agent of the present invention, in order to further increase the voltage maintenance ratio of the liquid crystal cell, tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure is preferably used as the fourth reaction with the diamine component. Carboxylic dianhydride. -25- 201132745 The tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure is exemplified by 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,3·dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro- 1-naphthalene succinic dianhydride, [4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride], 1,2 , 3,4-butane tetracarboxylic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid Acid dianhydride, tricyclo[4.2.1.02.5] decane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo[6.6.0.12, 7.03, 6.19, 14.010.13] Hexadecane-4,5,11,12-tetracarboxyindole-4,5:11,12-dianhydride and the like. Among them, in particular, when 1,2,3,4-cyclobutanetetracarboxylic dianhydride is used, an alignment film having excellent liquid crystal alignment property can be obtained, which is preferable. Further, when aromatic tetracarboxylic dianhydride is used, the liquid crystal alignment property can be improved, and the cumulative charge of the liquid crystal cell can be accelerated. The aromatic tetracarboxylic dianhydride is exemplified by pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2 ',3,3 '-biphenyltetracarboxylic acid Anhydride, 2,3,3 ' 4 _biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4-diphenyl Ketotetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,2,5,6-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like. Among them, pyromellitic dianhydride is preferred. Considering the solubility of the obtained polyaminic acid or polyimine, the balance of various properties such as liquid crystal alignment -26-201132745, voltage maintenance rate, and accumulated charge, 'tetracarboxylic acid II having an alicyclic structure or an aliphatic structure The use ratio of the anhydride to the aromatic tetracarboxylic dianhydride is preferably 90/10 to 50/50, more preferably 80/20 to 60/40. <Polymerization reaction> In the present invention, the polymerization reaction method of the tetracarboxylic dianhydride component and the diamine component is not particularly limited. In general, the polymerization can be carried out by mixing in an organic solvent to form polylysine, which can be converted into a polyimine by dehydrating and blocking the polyamic acid. A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent is a solution obtained by stirring or dissolving a diamine component in an organic solvent, and directly adding or dispersing a tetracarboxylic dianhydride component or a method of dissolving in an organic solvent, and conversely adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, and mutually adding a tetracarboxylic dianhydride component and a diamine The method of ingredients. Further, when the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of compounds, the polymerization reaction may be carried out by mixing the plurality of components in advance, or the polymerization may be carried out in an orderly manner. The temperature at which the tetracarboxylic dianhydride and the diamine component are polymerized in an organic solvent is usually 〇 150 ° C, preferably 5 to 100 ° C, more preferably 10 to 80 ° C. When the temperature is high, the polymerization reaction ends early, but when it is too high, there is a case where a polymer having a high molecular weight cannot be obtained. Further, the polymerization reaction can be carried out at any concentration, but it is difficult to obtain a polymer having a high molecular weight when the total concentration of the tetracarboxylic dianhydride and the amine component of the second -27-201132745 is too low, and the viscosity of the reaction liquid is too high when the concentration is too high, resulting in difficulty in the reaction. The mixture is uniformly stirred, so that the total concentration is preferably 50% by mass, more preferably 5 to 30% by mass. The initial stage of the polymerization can also be carried out at a high concentration, followed by the addition of an organic solvent. The organic solvent used in the above polymerization reaction is not particularly limited as long as it dissolves the produced polyaminic acid. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 1,3-dimethylimidazolidone, etc. . These may be used alone or in combination. Further, even a solvent in which polylysine cannot be dissolved can be used in the above solvent without being precipitated in the range in which the produced polyaminic acid is precipitated. Further, since the water in the organic solvent is a cause of hindering the polymerization reaction and further hydrolyzing the produced polylysine, the organic solvent is used as far as possible for dehydration. The ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization of polylysine is preferably 1: 0.8~1: 1.2, and the closer the molar ratio is to 1:1, the resulting poly The molecular weight of the proline acid becomes large. By controlling the molecular weight of the polyamine, the molecular weight of the polyamine obtained after the imidization can be adjusted. The molecular weight of the poly-proline or the polyimine of the present invention is not particularly limited, but when it is contained in a liquid crystal alignment treatment agent, the weight of the obtained coating film and the operation as a liquid crystal alignment treatment agent are easy. The average molecular weight is preferably from 2,000 to 200,000, more preferably from 5,000 to 50,000. -28-201132745 <Synthesis of Polyimine> The polyimine used in the liquid crystal alignment treatment agent of the present invention is a polyimine obtained by subjecting the above polyamine to ruthenium. The imidization of the polyaminic acid can be carried out by stirring in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 100 hours. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has an appropriate basicity for carrying out the reaction. Further, the acid liver may be, for example, acetic acid, trimellitic anhydride or pyromellitic anhydride. Among them, after the end of the imidization of acetic anhydride, the purification of the obtained polyimine is easy and preferable. As the organic solvent, the solvent used in the polymerization of the above polylysine may be used. The yield of the hydrazine imine may be controlled by adjusting the amount of the catalyst, the reaction temperature, the reaction time, and the like. The amount of the alkaline catalyst at this time is preferably from 0.2 to 10 moles, more preferably from 0.5 to 5 moles, of the amidoxime group. Further, the amount of the acid anhydride is preferably from 1 to 30 moles, more preferably from 1 to 10 moles, per mole of the amidate group. The reaction temperature is preferably from -20 to 25 ° C, more preferably from 0 to 180 ° C. The ruthenium imidization ratio of the polyimine used in the liquid crystal alignment treatment agent of the present invention is not particularly limited, but the ruthenium imidation ratio is preferably 40 based on the reason of obtaining a liquid crystal alignment film having a higher voltage maintenance ratio. More than %, more preferably 60% or more, and most preferably 80% or more. The solution of the polyimine thus obtained is used as a liquid crystal alignment agent, and is preferably used after the liquid crystal alignment treatment agent is recovered and washed -29-201132745. The polyimine is recovered by pouring the ruthenium solution into a weak solvent under stirring and filtering after precipitation of the polyimide. The weak solvent at this time may be exemplified by methanol 'acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like. The washing of the recovered polyimine can also be carried out with the weak solvent. The polyimine which is thus recovered and washed can be dried to a powder under normal pressure or reduced pressure at a constant temperature or heat. These operations can also be carried out on the aforementioned polylysine. For example, when the solvent used for the polymerization of the polyamic acid is not contained in the liquid crystal alignment treatment agent, or when the unreacted monomer component or impurities in the reaction solution are removed, the above-mentioned precipitation recovery and purification can be performed. Treatment agent> The liquid crystal alignment treatment agent of the present invention is a coating liquid containing at least one of a polyamic acid and a polyimine obtained as described above. In the case of the production example, the reaction solution of the polylysine or the polyimine may be directly or diluted, or the precipitate from the reaction solution may be redissolved in an organic solvent. Further, in the 'dilution or redissolution step', the solvent composition adjustment for controlling the coatability of the substrate or the addition of the additive for improving the film properties can be performed. Further, other resins which are mixed with a solution of a polyimine solution or a polyamic acid of a different structure as described above may be added. The organic solvent used in the above-mentioned dilution or redissolution step is not particularly limited as long as the polymer contained therein is dissolved. Specific examples thereof are N,N-dimethylformamide, hydrazine, hydrazine dimethylacetamide, N-methyl-2-pyrrolidone, -30-201132745 N-methyl caprolactam, 2 -pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 1,3 - Dimethylimidazolidinone and the like. Among them, Ν-methyl-2-pyrrolidone, Ν-ethyl-2-pyrrolidone, l,3-dimethylimidazolidone, and γ-butyrolactone are suitable. These may be used alone or in combination of two or more. The solvent added to control the applicability of the liquid crystal alignment agent to the substrate is exemplified by ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, and ethylene. Alcohol, b-methoxy-2-propanol ' 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, diethylene glycol II Ethyl ether, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-ethyl Acid ester, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. The solvent may contain a solvent which does not dissolve polyphosphoric acid or polyimine alone, but may be mixed in the liquid crystal alignment agent of the present invention as long as it does not precipitate the polymer. In particular, by appropriately mixing a solvent having a low surface tension, the uniformity of the coating film at the time of coating the substrate can be improved, and it can also be suitably used in the liquid crystal alignment treatment agent of the present invention. Among them, in particular, from the viewpoint of solubility of polyimine, butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether, and diethylene glycol diethyl ether are preferable. Additives for improving film properties are exemplified by 3-aminopropylmethyldiethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, (Aminoethylaminomethyl) phenethyltrimethoxyindole-31 - 201132745 Alkane and other decane coupling agent. When the decane coupling agent is added, the adhesion of the coating film to the substrate can be improved. However, when the amount is too large, aggregation of polyamine or polyimine is likely to occur. Therefore, the content of the decane coupling agent is preferably from 0.5 to 10% by mass, more preferably from 1 to 5 % by mass, based on the total mass of the polyamic acid and the polyimine. The solid content concentration of the liquid crystal alignment agent of the present invention can be appropriately changed depending on the setting of the thickness of the liquid crystal alignment film to be formed, but is preferably from 1 to 10% by mass. When it is less than 1% by mass, it is difficult to form a uniform and defect-free coating film, and when it is more than 10% by mass, the solution storage stability may be deteriorated. The solid component referred to herein means a solvent which is removed from the liquid crystal alignment agent. Further, the concentration of the polyamic acid or the polyimine used in the liquid crystal alignment agent of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably from the viewpoint of the characteristics of the obtained liquid crystal alignment film. It is 3% by mass or more, preferably 5% by mass or more. The liquid crystal alignment treatment agent obtained above is preferably passed through a furnace before being applied to a substrate. <Liquid crystal display device> The liquid crystal alignment agent of the present invention can be applied onto a substrate, dried, and fired to form a coating film, and the coating film surface is rubbed and treated to be used as a liquid crystal alignment film for rubbing. Alternatively, it may be used as a VA (for vertical alignment) liquid crystal alignment film or a photo alignment film without rubbing treatment. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used, and a liquid crystal drive is used in view of simplification of the process. 32-201132745 It is preferable to use a substrate such as an ITO electrode. Further, the reflective liquid crystal display device may use an opaque material such as a germanium wafer only on a substrate on one side, and in this case, a material that reflects light such as aluminum may be used as the electrode. The coating method of the liquid crystal alignment treatment agent is exemplified by a spin coating method, a printing method, an inkjet method, etc., but in terms of productivity, a soft printing method is widely used in the industry, and is also suitable for the liquid crystal alignment treatment of the present invention. Agent. The drying step after the application of the liquid crystal alignment treatment agent is not necessarily required, but the drying step is preferably carried out when the time from the application of the coating to the time of firing is not necessarily performed for each of the substrates, or when it is not immediately fired after coating. Drying is preferred to evaporate the solvent to such an extent that the shape of the coating film is not deformed by the transport of the substrate, and the drying means is not particularly limited, and is, for example, a hot plate of 50 to 150 ° C, preferably 80 to 120 ° C. Dry for 0.5 to 30 minutes, preferably for 1 to 5 minutes. The firing of the substrate coated with the liquid crystal alignment agent is preferably carried out at any temperature of from 100 to 3 50 ° C, more preferably from 150 to 300 ° C, still more preferably from 18 0 to 250 ° C. When the proline group is present in the liquid crystal alignment agent, the conversion ratio of the conversion of the proline to the quinone is changed depending on the firing, but the liquid crystal alignment agent of the present invention does not necessarily need to be imidized by 100%. When the thickness of the coating film after firing is too thick, the power consumption of the liquid crystal display element is unfavorable. When the thickness of the liquid crystal display element is too small, the reliability of the liquid crystal display element is lowered, so that it is preferably from 10 to 200 nm, more preferably from 50 to 100 nm. As the above-described rubbing treatment of the coating film formed on the substrate, a conventional friction device can be used. The material of the rubbing cloth at this time is exemplified by cotton, enamel, nylon, etc. The substrate to which the liquid crystal alignment film is attached by the above-mentioned method can be produced by the method of the present invention, and the liquid crystal cell is produced as an example of the liquid crystal display element. Generally, a method of forming a liquid crystal alignment alcohol of 1 to 30 μm, more preferably 2 to 10 μm, and maintaining the direction of any angle of 〇2 to 27°, and sealing it with a dense liquid crystal is used. The method of encapsulating the liquid crystal is shown as a drop-in (ODF) method in which the liquid crystal is produced by intracellular pressure reduction, and then liquid crystal is injected. The liquid crystal display element thus obtained is used in various types of display elements such as 5, STN liquid crystal display elements, TFT liquid crystal display elements, and lateral electric field type (IPS) liquid crystal display elements. EXAMPLES Examples are given below, and the explanation is explained in more detail to be limited to these. (Synthesis Example 1) Synthesis of 3,5-diaminobenzyl benzoate in a 500 mL four-necked flask, 20.0 g of pyridine nitrobenzyl alcohol, 14.9 g of benzamidine chloride, in a solution at room temperature Stir for 30 hours. The reaction mixture was stirred for 1 hour. The organic hydrazine was extracted with ethyl acetate. The aqueous sodium hydrogencarbonate solution and the saturated aqueous sodium chloride solution were added to the organic layer to be dehydrated and dried, and filtered. If the liquid crystal cell is produced: one of the pair of substrates is preferably used so that the rubbing direction is fixed around the sealing agent, the injection is not particularly limited, and the vacuum method of the crystal can be exemplified, and the dropping liquid is used as the liquid crystal display element element, Ο C Β liquid crystal display R element, VA liquid crystal display invention, but the invention should not add 8.8g to the solution containing 3,5-ditetrahydrofuran 150mL, add pure water 50 m LI, 1N hydrochloric acid, saturated layer . Anhydrous magnesium sulfate was distilled off using a rotary evaporator at -34 - 201132745. The residue was recrystallized using ethyl acetate to synthesize 24.9 g of a dinitro compound having the following NMR characteristics (yield: 82%). 'H NMR (400 MHz, CDC13): δ 9.03 (t, 1H), 8.65 (d, 2H), 8.12-8.07 (m, 2H), 7.63 (tt, 1H), 7.5 3-7.47 (m, 2H) , 5.55 (s, 2H). [Chem. 17]

24.9 g of a dinitro compound, 2.5 g of uranium/carbon, and 250 g of 1,4-dioxane were placed in a 500 mL four-necked flask, and the mixture was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, the diatomaceous earth was filtered. The solvent was purged using a rotary evaporator. The residue was recrystallized using methanol to synthesize 12.8 g of a thin brown solid (yield 64%). The results of the NMR measurement of the thin brown solid are shown below. From the results, it was confirmed that the obtained thin brown solid was the intended diamine compound. NMR NMR (4 0 0 Μ H z, DMS Ο - d 6 ) : δ 8.0 1 - 7.9 9 (m, 2 Η), 7.6 9 7.64 (m, 1 Η), 7.57-7.51 (m, 2H), 5.87 (d, 2H), 5.79 (t, 1H), 5.06 (s, 2H), 4.80 (br, 4H). [Chem. 18]

201132745 (Synthesis Example 2) Synthesis of 3, 5-diaminobenzyl nicotinic acid ester In a 500 mL three-necked flask, 25.0 g of 1,3-dinitrobenzyl alcohol and 24.6 g of pyridinium chloride hydrochloride were added. N, N-dimethylaminopyridine 1.4 g, tetrahydrofuran 300 mL. 52.8 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 18 hours. After completion of the reaction, 50 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and brine. Anhydrous magnesium sulfate was added to the organic layer to dehydrate and dry, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized using tetrahydrofuran / hexane = 1/4 to synthesize 36.0 g of a dinitro compound having the following NMR characteristics (yield: 94%). 'H NMR (400 MHz, CDC13): δ 9.04 (t, 1H), 8.83 -8.79 (m, 1H), 8.71-8.65 (m, 2H), 8.19 (dt, 1H), 7.91 (d, 1H), 7.59-7.54 (m, 1H), 5.64 (d, 2H). [Chem. 19]

To a 500 mL four-necked flask, 29.4 g of a dinitro compound, 4.5 g of ruthenium/carbon, and 430 g of 1,4-dioxane were added, and the mixture was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, the diatomaceous earth was filtered, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using isopropyl alcohol to synthesize 20.2 g of a thin brown solid (yield 86%). -36- 201132745 The result of the NMR measurement of the thin brown solid is shown below. From the results, it was confirmed that the obtained thin brown solid was the intended diamine compound. 'H NMR (400 MHz, CDC13): δ 8.80-8.76 (m, 1 Η), 8.14 (dt, 1H), 7.83 (dt, 1H), 7.50-7.45 (m, 1H), 6.23 (d, 2H) , 6.00 (t, 1H), 5.28 (s, 2H), 3.1 (br, 4H). [Chem. 20]

(Synthesis Example 3) Synthesis of 3,5-diaminobenzyl-1,3,4-trimethylpyrazole-5-carboxylate Addition of 1,3,4-trimethyl to a 500 mL four-necked flask 17.1 g of benzyl-1H-pyrazole-5-carboxylic acid and 250 mL of dichloromethane were cooled to a temperature of 0 degree. 10.2 mL of grass dichloride, 0.8 g of DMF was added, and the mixture was stirred at room temperature for 2 hours. After stirring, 22.0 g of 3,5-dinitrobenzyl alcohol and 9.7 g of pyridine were added, and the mixture was stirred at room temperature for 41 hours. After the reaction was completed, 50 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and brine. Anhydrous magnesium sulfate was added to the organic layer to dehydrate and dry, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized using isopropyl alcohol to obtain 18.1 g of a dinitro compound having the following NMR characteristics (yield 71%). 'H NMR (400 MHz, CDC13): δ 9.04 (t, 1H), 8.64 (dt, 2H), 5.54 (t, 2H), 4.08 (s, 3H), 2.24 (s, 3H), 2.21 (s, 3H) -37- 201132745 [Chem. 21]

A dinitro compound 18.8 g, platinum/carbon 1.8 g, and tetrahydrofuran (180 g) were added to a 500 mL four-necked flask, and the mixture was stirred under a hydrogen atmosphere for 1 hour. After completion of the reaction, the mixture was filtered through Celite, and then evaporated on a rotary evaporator. &lt;RTI ID=0.0&gt;&gt;&gt; The results of the NMR measurement of the thin brown solid are shown below. The result is a diamine compound for the purpose of obtaining a thin brown solid. 1 Η) 'Η NMR (400 MHz, CDC13) : δ 6.15 (d, 2H), 5.98 (t, 5.15 (s, 2H), 4.06 (s, 3H), 3.58 (br, 4H), 2.18 (s, 6H) 0 [Chem. 22]

(Synthesis Example 4) Synthesis of 2-(pyridin-2-yl)ethyl-3,5-diaminoester benzoate in a 300 mL four-necked flask, 2-pyridine ethanol 23.4 5 g, triethylamine 19.23 g is dissolved in 200 mL of tetrahydrofuran, and cooled to 10 ° C or less. 'Bian-38-201132745 A solution obtained by dissolving 41.68 g of dinitrobenzhydryl chloride in tetrahydrofuran 〇 〇g was added dropwise. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction, the reaction solution was poured into 1.5 L of distilled water, and the precipitated solid was filtered, washed with water, and then washed with ethanol 380 g to obtain 50.82 g of dinitro group having the following NMR characteristics. Compound (yield: 89%). 1HNMR (400MHz, DMSO-d6) : δ 9.76 (t, 1 Η) 9.09-9.02 (m, 2H), 8.99-8.93 (m, lH), 8.50 (m, lH), 7.64-7.60 (m, iH) , 7.3 6-7.3 2 (m, lH), 4.57 (s, 2H), 3.35 (s, 2H)» [Chem. 23]

A mixture of 48.00 g of a dinitro compound, 4.8 g of platinum carbon, and 490 g of 1,4-dioxane was stirred at 23 ° C under a hydrogen atmosphere. After completion of the reaction, the catalyst was filtered with diatomaceous earth, and then the solvent was distilled off with an evaporator to obtain a crude product. The crude product was washed away by dispersing ethanol (300 g) to obtain the objective diamine compound (yield: 27.20 g, yield: 70%). 'HNMR (400MHz, DMSO-d6): 5 8.64 (t, 1 Η), 8.44 (d, 1 Η), 7.67 (d,lH), 7_34 (q,lH), 6.23 (d,2H),5· 94 (S, 1H), 4.87 (b, 4H), 4.39 (d, 2H), 3.38 (s, 2H). -39 - 201132745 [Chem. 24]

1,4-dioxane 60°C H2N

Example 10 and Comparative Examples 1 to 4 In the following Examples 1 to 10 and Comparative Examples 1 to 4, the production examples of the liquid crystal alignment treatment agent were described, but the synthesis of polyacrylic acid and polyimine was used. The following is a description of &lt;measurement of molecular weight&gt;, &lt;measurement of yttrium imidation rate&gt;, &lt;evaluation of friction resistance&gt;, &lt;production of liquid crystal cell&gt;&gt; The method of evaluating the inclination angle &gt;, &lt;measurement method of voltage maintenance rate&gt;, and &lt;evaluation of accumulated electric charge (RDC)&gt; is as follows. Further, the physical properties (characteristics) of the respective liquid crystal alignment treatment agents of the examples and the comparative examples are shown in Tables 1 and 2 which will be described later. <tetracarboxylic dianhydride> CBDA : 1,2,3,4-cyclobutane tetracarboxylic dianhydride <diamine> DABPh: 3,5-diaminobenzyl benzoate 0 8 8: smoke Alkaline acid 3,5-diaminobenzyl DABTMPz: 3,5-diamino-based 1,3,4-trimethyl-1H-0-pyrazole-5-carboxylate 1^[0 : 2,5-diaminobenzoic acid 2-(pyridine.2-yl)ethyl ester C14DAB: 4-tetradecyloxy-1,3-diaminobenzene 3-ABA: 3-aminobenzylamine -40- 201132745 <Organic solvent> NMP : N-methyl-2-pyrrolidone γ Β : γ-butyrolactone BC : butyl cellosolve DPM : dipropylene glycol monomethyl ether <Determination of molecular weight> Polylysine and polypeptone The molecular weight of the imine is measured by the Gpc (normal temperature gel permeation chromatography) apparatus described below, and the number average molecular weight and the weight average are calculated by converting polyethylene glycol and polyethylene oxide. Molecular weight. GPC device: manufactured by Shodex (GPC-101) Pipe column: manufactured by Shodex (KD803, KD805 series)

Column temperature: 50 °C Dissolution: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr.H20) is 30 mmol/L, phosphoric acid. Anhydrous crystal (〇_phosphoric acid) is 30 mmol /L, tetrahydrofuran (THF) is 10mI / L) Flow rate: 1.0 mL / min calibration line standard sample for production: TSK standard polyethylene oxide manufactured by TOSHO company (number average molecular weight of about 900,000, 1 500,000, 1 00,000 , 30,0 00 ), and polyethylene glycol (weight average molecular weight of about 〇〇〇2, 〇〇〇, 4,000, 1,000) manufactured by Polymer Laboratories. -41 - 201132745 <Determination of the imidization rate of oxime> The imidization ratio of polyimine is dissolved in d6-DMSO (dimethyl sulfonium-d6), and 1H-NMR is measured. Calculated by the ratio of the cumulative enthalpy of the proton peak to the ratio of the proline group remaining without imidization. <Evaluation of friction resistance> Each liquid crystal alignment treatment agent was spin-coated on a glass substrate to which a transparent electrode was attached. After drying on a hot plate of 8 (TC) for 5 minutes, it was baked on a hot plate at 210 ° C for 10 minutes to form a coating film having a film thickness of 70 nm. A friction device having a roll diameter of 120 mm (RS01 manufactured by Iijima Gauge Co., Ltd.) -2 type), using a crepe cloth, rubbing the surface of the film with a roller rotation number of 100 rpm, a roller speed of 50 mm/sec, and a pushing amount of 0.5 mm to obtain a substrate to which a liquid crystal alignment film is attached. The surface of the liquid crystal alignment film was observed. The evaluation was based on the following criteria: 〇: no slag or friction scar was observed Δ: slag or friction scar was observed X: film peeling or visual observation of friction scars <production of liquid crystal cells> Each liquid crystal alignment treatment agent is produced as follows Liquid crystal cells. Each liquid crystal alignment treatment agent was spin-coated on a glass substrate to which a transparent electrode was attached, and dried on a hot plate at 80 ° C for 5 minutes, and then fired on a hot plate at 210 ° C for 1 minute. A coating film having a film thickness of 70 nm was formed, and a rubbing device having a roll diameter of -42 - 201132745 120 mm was used, and a crepe cloth was used, and the number of rolls was i rpm, the speed of the roll was 50 mm/sec, and the amount of squeezing was 3 mm. Rubbing the surface of the coating film to obtain a substrate to which the liquid crystal alignment film is attached. Two substrates to which the liquid crystal alignment film is attached are prepared, and a spacer of 6 μm is spread on one of the liquid crystal alignment film faces, and a sealant is printed thereon, and After the other substrate is bonded such that the liquid crystal alignment film faces and the rubbing direction is perpendicular, the sealing agent is hardened to form a hollow cell. The liquid crystal MLC - 2 0 0 3 is injected into the hollow cell by a vacuum injection method. (manufactured by Merck, Japan), the injection port is closed, and the twisted nematic liquid crystal cell is obtained. <Measurement of pretilt angle> Heating at 1 〇 5 t is produced by the method described in <Liquid cell fabrication> above. Twisted nematic liquid crystal After 5 minutes, the measurement of the pretilt angle and the measurement of the voltage maintenance rate were carried out. The pretilt angle was measured by the crystal rotation method. <Measurement of voltage holding ratio> The twisted nematic direction produced by the method described in the above <Liquid cell production> The liquid crystal cell was applied with a voltage of 60 μδ at a temperature of 90 ° C, and a voltage of 16.67 ms was measured to determine how much voltage can be maintained as a voltage maintenance ratio. Further, the voltage maintenance rate is measured using a voltage maintenance ratio. Device (manufactured by Toyo Corporation, VHR-1). <Evaluation of Accumulated Charge (RDC)> The twisted-to-43-201132745 column type liquid crystal cell produced by the method described in the above <Liquid Cell Production>, at 2 3 At a temperature of ° C, a DC voltage was applied from 〇V to 1.0 V at a 0.1 V interval, and the Flicker Amplitude level at each voltage was measured to prepare a correction line. Next, after grounding for 5 minutes, an AC voltage of 3.0 V and a DC voltage of 5.0 V were applied, and the scintillation amplitude level after 1 hour was measured, and the RDC was evaluated by comparison with a calibration line prepared in advance. The evaluation method of this RDC is called a scintillation reference method. (Example 1) 5.00 g (25 mmol) of CBDA was used as a tetracarboxylic dianhydride component, and 6.30 g (26 mmol) of DABPh was used as a diamine component, and reacted in NMP 45.18 g at room temperature for 16 hours to obtain 20% by mass. Poly-proline solution (PAA-1). 10.0 g of the polyamic acid solution (PAA-1) was diluted with NMP 13.3 g and BC l〇.〇g to obtain a liquid crystal alignment composed of a solution containing 6 mass% solid content, 64 mass% NMP, and 30 mass% BC. Treatment agent. (Example 2) 93.33 g of NMP was added to 40 g of the polyamic acid solution (PAA-1 concentration: 20% by mass) obtained in Example 1, and diluted, followed by the addition of 5.64 g of acetic anhydride and 2.33 g of pyridine, at 4 ( The TC was reacted for 3 hours to carry out hydrazine imidization. After the reaction solution was cooled to about room temperature, it was poured into methanol 500 ml, and the precipitated solid matter was recovered. Then, after washing the solid matter several times with methanol, Drying under reduced pressure at 10 ° C to obtain a white powder of polyimine (SPI-1). The number average molecular weight of the polyimine is 14,630, and the weight average molecular weight is -44-201132745 3 2,1 60 Further, '醯imination rate was 8 2 % ° 18.0 g of γ-BL was added to the obtained polyamidimide (SPI-1) 2.00 g, and stirred at 5 (TC for 2 hours). At the time, the polyimine was completely dissolved. Then, 8.0 g of γ-BL, 6.00 g of BC, and 6.00 g of DPM were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyfluorene containing 5 mass··. A liquid crystal alignment treatment agent consisting of a solution of imine (SPI-1), 65 masses of 15 mass% 2DPM, and 15 mass% of BC. (Example 3) 5.00 g (25 mmol) of CBDA was used as Residual acid dioxime: l: component, 6,32 g (26 mmol) of DABPy as a diamine component, reacted in NMP 45_29g at room temperature for 16 hours to obtain 20% by mass of poly-proline solution (PAA-2) The polyamic acid solution (PAA-2) 10.〇g was diluted with NMP 13.3g and BC lO.Og to obtain a solution containing 6 mass% solid content, 64 mass% NMP and 30 mass% BC. Liquid crystal alignment treatment agent. (Example 4) 93.3 g of NMP was added to 40 g of the polyamic acid solution (PAA-2 concentration: 20% by mass) obtained in Example 3, and then diluted, followed by the addition of 5.77 g of acetic anhydride and pyridine. 2.39 g, the imidization was carried out by reacting for 3 hours at 40 ° C. After cooling the reaction solution to about room temperature, it was poured into 500 mL of methanol to recover the precipitated solid matter. Then, the solid matter was washed several times with methanol. Thereafter, it was dried under reduced pressure at 100 ° C to obtain a white powder of polyimine (SPI-2). The number average molecular weight of the polyethylenimine was -13,204' and the weight average molecular weight was 30,700. The sulfhydrylation rate was 87%. 18.0 g of γ-BL was added to the obtained polyamidimide (SPI-2) 2.00 g, and stirred at 50 °C. 20 hours. At the end of the stirring, the polyimine was completely dissolved. Then, 8.0 g of γ-BL, 6.00 g of BC and 6.00 g of DPM were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain A liquid crystal alignment treatment agent comprising a solution of 5 mass% of polyimine (SPI-2), 65 mass% of γ-BL, 15 mass% of 2DPM, and 15 mass% of BC. (Example 5) 5.30 g (27 mmol) of CBDA was used as a tetracarboxylic dianhydride component, 2.00 g (8 mmol) of DABPh, 1.35 g (1 mmol) of 3-ABA and 2.65 g (8 mmol). C14DAB was reacted as a diamine component in NMP 45.25 g at room temperature for 16 hours to obtain 20 mass%. Poly-proline solution (PAA-3). The polyamino acid solution (PAA-3) was diluted 10.0 g with NMP 13.3 g and BC 10.0 g to obtain a content of 6 mass. /. A liquid crystal alignment treatment agent composed of a solid matter, a solution of 64% by mass of NMP and 30% by mass of BC. (Example 6) 93.3 3 g of NMP was added to 40 g of the polyamic acid solution (PAA-3 concentration: 20% by mass) obtained in Example 5, followed by the addition of acetic anhydride (5.97 g and pyridine 2.47 g'). The hydrazine imidization was carried out by reacting at 60 ° C for 3 hours. The reaction solution was allowed to cool to about room temperature, and then poured into methanol at 50,000 m to recover the solid matter of the precipitate -46-201132745. Then, after washing the solid matter with methanol several times, it was dried under reduced pressure to obtain a milky white powder of polyimine (SPI-3). The number average molecular weight of the polyimine was 14,785 ' The weight average molecular weight was 3,7 8 3 3. Further, the oxime imidization ratio was 88%. 18.0 g of γ-BL was added to the obtained polyimine (SPI-3) 2.00 g at 50 The mixture was stirred for 20 hours at ° C. At the end of the stirring, the polyimine was completely dissolved. Then, 8.0 g of γ-BL, 6.00 g of BC and 6.00 g of DPM were added to the solution, and the mixture was stirred at 50 ° C for 2 hours. 'A liquid crystal alignment treatment agent comprising a solution of 5 mass% polyimine (SPI-3), 65 mass% of 丫-8!^, 15 mass% of DPM, and 15 mass% of BC was obtained. 7) 5.27 g (27 mmol) of CBDA was used as the tetracarboxylic dianhydride component, 2.00 g (8 mmol) of DABPy, 1.34 g (ll mmol) of 3-ABA and 2.63 g (8 mmol) of C14DAB as the diamine component in NMP. In 44.96 g, the reaction was carried out at room temperature for 16 hours to obtain 20% by mass of a polyaminic acid solution (PAA-4). The polyaminic acid solution (PAA-4) was diluted with NMP 13.3 g and BClO.Og. .Og, obtained by A liquid crystal alignment treatment agent having a composition of 6 mass% solid content '64 mass% NMP and 30 mass% BC. (Example 8) 93.3 3 g of NMP was added to the polyamine solution obtained in Example 7 ( PAA-4 concentration: 20% by mass) was diluted in 40 g, and then acetic anhydride-47-201132745 5.97 g and pyridine 2.47 g were added, and the reaction was carried out at 60 ° C for 3 hours to carry out hydrazine imidization. The reaction solution was cooled to room temperature. Thereafter, the mixture was poured into methanol of 500 ml, and the precipitated solid matter was recovered. Then, the solid matter was washed with methanol several times, and then dried under reduced pressure at 10 ° C to obtain polyimine (SPI-4). Milky white powder. The number average molecular weight of the polyimine is 15,5 94, the weight average molecular weight is 4 2, 3 2 0 ' and the imidization ratio is 87%. Adding 18.0 g of γ-BL In the obtained polyimine (SPI-4) 2.00 g, the mixture was stirred at 50 ° C for 20 hours. At the end of the kneading, the polyimine was completely dissolved. Then, 8.0 g of γ-BL was added to the solution. 6.00 g of BC and 6.00 g of DPM were stirred at 50 ° C for 20 hours to obtain γ-BL, 15 mass by mass of yttrium imine (SPI-4) containing 5% by mass. The liquid crystal composition of DPM and 15 mass% of the BC solution alignment treating agent. (Example 9) 5.57 g (29 mmol) of CBDA was used as a component of tetradecanoic acid, 2 to 38 g (9 mmol) of DABTMPz, 1.4 2 g (1 2 mm ο 1 ) of 3-ABA and 2.79 g (9 mmoI). C 1 4DAB was reacted as a diamine component in NΜP 46.7 g at room temperature for 16 hours to obtain a polyamine acid solution (PAA-5) having a concentration of 20% by mass. The polyamic acid solution (PAA-5) 10.Og was diluted with NMP 13.3g and BC 10.〇g, and obtained by containing 6% by mass of polyaminic acid (PAA-5), 64% by mass of NMP, and 30% by mass. Liquid crystal alignment treatment agent of BC solution composition - 48 - 201132745 (Example 1 〇) 93.3 g of NMP was added to the polyacrylic acid (PAA-5 ) solution obtained in the same manner as in Example 9 (PAA-5 concentration 20 mass) %) was diluted in 40.0 g, and 6.06 g of acetic anhydride and 2·5 3 g of pyridine were added, and the reaction was carried out for 6 hours at TC for 3 hours. After cooling the reaction solution to about room temperature, 500 mL of methanol was poured. The precipitated solid matter was recovered, and the solid matter was washed twice with methanol, and then dried under reduced pressure at 100 ° C to obtain a white tan powder of polyimine (SPI-5). The number average molecular weight was 14,222, and the weight average molecular weight was 33,154. Further, the oxime imidization ratio was 88%. 18.0 g of γ-BL was added to the obtained polyimine (SPI-5) 2.00 g, Stir at 50 ° C for 20 hours. At the end of the stirring, the polyimine was completely dissolved. Then, 8.00 g of γ-BL, 6.00 g of BC and 6.00 g of DPM were added to the solution, at 5 After stirring at 0 ° C for 20 hours, it was obtained by a solution containing 5% by mass of polyimine (SPI-5), 65 mass% of γ-BL, 15 mass%/〇 of DPM, and 15 mass% of BC. Liquid crystal alignment treatment agent (Comparative Example 1) 12.5 g (64 mmol) of CBDA was used as a tetracarboxylic dianhydride component, 5.56 g (46 mmol) of 3 - ABA and 6 · 2 5 g (20 mm ο 1 ) of C14DAB. As a diamine component, a reaction of 'reaction at room temperature for 16 hours' in NMP 97.20g yielded 20 masses. /〇 Polylysine solution (PAA-6) ° Diluted the polyamine with NMP 13.3g and BC lO.Og 10.0 g of an acid solution (PAA-6), a liquid crystal alignment treatment agent consisting of a solution containing 6 mass% of solids, 64 mass% of NMP, and 30 mass% of BC was obtained. -49 - 201132745 (Comparative Example 2) 1 16.67 g of NMP was added to 50 g of the polyamic acid solution (PAA-6) obtained in Comparative Example 1, and diluted, and 7.39 g of acetic anhydride and 3.15 g of pyridine were added, and the reaction was carried out at 70 ° C for 3 hours to carry out hydrazine imidization, but In the reaction, gelatinization was carried out. Further, 116.67 g of NMP was added to 50 g of polylysine solution (PAA-6) to be diluted, and 7.39 g of acetic anhydride and 3.15 g of pyridine were added to iodide. Temperature of 50 ° C. After the reaction solution was cooled to about room temperature, it was poured into 600 ml of methanol to recover a precipitated solid. Subsequently, the solid matter was washed with methanol several times, and then dried under reduced pressure at 10 ° C to obtain a white powder of polyethylenimine (SPI-6). The polyimine had a number average molecular weight of 16,338 and a weight average molecular weight of 399,86. The yield of hydrazine was 80%. 9 g of γ-BL was added to polyimine (SPI-6), 〇〇g, and stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Next, 4.0 g of γ-BL, 3.0 g of BC, and 3.0 g of DPM were added to the solution, and the mixture was stirred at 50 t for 20 hours to obtain γ-BL, which was contained in an amount of 5% by mass, and 5% by mass. A liquid crystal alignment treatment agent comprising a solution of 5 mass% DP Μ and 15 mass% BC. (Comparative Example 3) 5.76 g (29 mmol) of CBDA was used as a tetracarboxylic dianhydride component, 2.31 g (9 mmol) of RefDA, 1.46 g (12 mmol) of 3_ABA, and 2.88 g (9 mmol) of C14DAB as a diamine component. In NMP 56.84g -50-201132745, it was reacted at room temperature for 16 hours to obtain a 20% by mass poly-proline solution (PAA-7). The polyamic acid solution (PAA-7) 1 O.Og was diluted with NMP 13.3g and BC lO.Og to obtain a liquid crystal alignment composed of a solution containing 6 mass% solids, 64 mass% NMP, and 30 mass% BC. Treatment agent. (Comparative Example 4) 1 1 6 · 6 7 g of Ν Μ P was added to 50 g of the polylysine solution (PAA-7) obtained in Comparative Example 3 to dilute it, and the addition of Q acetic anhydride 7.39 g and pyridine was added. 3.06 g was reacted at 70 ° C for 3 hours to carry out oxime imidization. After the reaction solution was cooled to about room temperature, it was poured into 600 mL of methanol to recover a precipitated solid. Next, the solid matter was washed with methanol several times, and then dried under reduced pressure to obtain a thin brown powder of polyimine (SPI-7). The number average molecular weight of the polyimine was 18,668, and the weight was 18. The average molecular weight was 41, 256. The oxime imidization ratio was 89%. 9 g of γ-BL was added to polyimine (SPI-7) l.〇〇g in '5 at TC for 20 hours. At the end of stirring At that time, the polyimine was completely dissolved. Then, 4.0 g of γ-BL, 3.0 g of BC, and 3.0 g of DPM were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a phthalocyanine containing 5% by mass. A liquid crystal alignment treatment agent comprising an amine, a 65 mass% γ-BL, a 15 mass% DP Μ, and a 15 mass% BC solution. [Industrial Applicability] By the liquid crystal alignment treatment agent of the present invention, It is possible to obtain a liquid crystal alignment film which is strong in peeling or reduction, has a high voltage holding ratio, and is difficult to cause initial charge accumulation even when a direct current voltage is applied, and is obtained by using the liquid crystal alignment treatment agent of the present invention. The liquid crystal display element can be a highly reliable liquid crystal display device suitable for TN liquid Display elements using various modes, such as a crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, a VA liquid crystal display element, an IPS liquid crystal display element, an OC liquid crystal display element, etc. m 1] Polylysine solution or polyimine oxime Amination rate [%] dianhydride component (mmol) diamine component (mmol) solid component (%) Example 1 PAA-1 CBDA (25) DABPh (26) 6.0 Example 2 SPI-1 82 CBDA (25) DABPh(26) 5.0 Example 3 PAA-2 - CBDA(25) DABPy(26) 6.0 Example 4 SPI-2 87 CBDA(25) DABP Fire 26) 5.0 Example 5 PAA-3 - CBDA(27) 3- ABA(ll), DABPh(8), C14DAB(8) 6.0 Example 6 SPI-3 88 CBDA(27) 3-ABA(ll), DABPh(8), C14DAB(8) 5.0 Example 7 PAA-4 - CBDA(27) 3-ABA(ll), DABPy(8), C14DAB(8) 6.0 Example 8 SPI-4 87 CBDA(27) 3-ABA(ll), DABPy(8), C14DAB(8) 5.0 Implementation Example 9 PAA-5 - CBDA(29) 3-ABA(12), DABTMPz(9) C14DAB(9) 6.0 Example 10 SPI-5 88 CBDA(29) 3-ABA(12), DABTMPz(9) C14DAB( 9) 5.0 Comparative Example 1 PAA-6 - CBDA(64) 3-ABA(46), C14DAB(20) 6.0 Comparative Example 2 SPI-6 80 CBDA(64) 3-ABA(46), C14DAB(20) 5.0 Comparison Example 3 PAA-7 - CBDA ( 29) 3-ABA(12), RefDA(9), C14DAB(9) 6.0 Comparative Example 4 SPI-7 89 CBDA(29) 3-ABA(12), RefDA (9), C14DAB(9) 5.0 -52- 201132745 [Table 2] Frictional resistance inclination angle [. Voltage maintenance rate [%] 90° 〇 RDCm Example 1 〇 0.7 90 0.24 Example 2 〇 0.8 92 0.20 Example 3 〇 1.0 92 0.23 Example 4 〇 1.2 93 0.17 Example 5 〇 6.1 92 0.25 Example 6 〇 3.1 94 0.21 Example 7 〇5.1 93 0.20 Example 8 〇 3.4 95 0.16 Example 9 〇 5.7 93 0.21 Example 10 〇 3.7 95 0.15 Comparative Example 1 Δ 4.5 87 0.50 Comparative Example 2 X 3.1 92 0.45 Comparative Example 3 Δ 4.7 90 0.30 Comparative Example 4 Δ 3.3 92 0.25 In addition, the entire contents of the specification, application scope and abstract of Japanese Patent Application No. 2000 9-2 8 3 3 3 0, filed on December 14, 2009, are incorporated herein by reference. As a disclosure of the present specification. -53-

Claims (1)

201132745 VII. Patent application scope: 1 . A liquid crystal alignment treatment agent containing a polyamine which is obtained by reacting a diamine component containing a diamine compound represented by the following formula [1] with a tetracarboxylic dianhydride component. At least one polymer selected from the group consisting of an acid and a polyimine obtained by subjecting the polyamic acid to ruthenium imidization, (In the formula, Ar represents a carbocyclic aromatic compound or a heterocyclic aromatic compound containing a nitrogen atom, and a hydrogen atom constituting a ring or a hydrogen atom of a nitrogen atom may be substituted). 2. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein Ar of the formula [1] is a carbocyclic aromatic compound of a six-membered ring or a heterocyclic aromatic compound of a nitrogen-containing atom of a six-membered ring. 3. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein Ar of the formula [1] is a heterocyclic aromatic compound having a nitrogen atom of a five-membered ring. 4. The liquid crystal alignment treatment agent according to claim 1, wherein A r of the formula [1] is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine. 5. The liquid crystal alignment treatment agent according to claim 1, wherein Ar of the formula [1] is oxazole, oxadiazole, thiazole, thiadiazole, pyrrole, imidazole, pyridyl or triterpene. 6. The liquid crystal alignment treatment agent of the first aspect of the invention, wherein the diamine compound represented by the formula [1] is any one of the compounds represented by the following general formulas [4] to [6] '-54-201132745 [ 2] 7. The liquid crystal alignment treatment agent according to the ninth aspect of the invention, wherein the amine compound is a compound represented by the following formula [2]: [Chemical Formula 3] 8. The liquid crystal alignment agent of any one of claims 1 to 7 wherein at least 10 mol% or more of the diamine compound represented by the following formula [3] is used as the diamine component: H2N-A r 1 -R, -N H-R2 [3] (wherein Ar' represents a phenyl or naphthyl group, 1^ represents an alkylene group having 1 to 5 carbon atoms, and R2 represents an alkyl group having 1 to 5 carbon atoms. ). The liquid crystal alignment treatment agent according to any one of claims 1 to 8, wherein the tetracarboxylic dianhydride component comprises a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment treatment agent according to any one of claims 1 to 9 to a substrate to which an electrode is attached, and firing. 1 1. A liquid crystal display element 'which is provided as in the patent application range 10 - 55 - Γ - Ar 201132745 liquid crystal alignment film. 12. A diamine compound represented by the following formula [1], wherein (Ar represents a carbocyclic aromatic compound or a heteroaromatic compound containing a nitrogen atom) and constitutes a ring of a carbon atom or The hydrogen atom on the nitrogen atom is substituted). 1 3 . The diamine compound according to claim 12, wherein Ar is a carbocyclic aromatic compound of a six-membered ring or a nitrogen-containing primary heterocyclic aromatic compound of a six-membered ring. A diamine compound according to claim 12, wherein Ar is a heterocyclic aromatic compound having a nitrogen atom of a five-membered ring. 1 5. A diamine compound according to claim 12, wherein Ar is benzene, pyridinium, azine, pentidine, pyrazine or trioxane. 1 6 · A diamine compound according to claim 12, wherein Ar is oxazole, oxadiazole, thiazide, thiadiazole, pyrolipid, imipenem, or triterpene. 1 7. The diamine compound according to the scope of claim 2, wherein the diamine compound represented by [1] is a compound represented by the following general formula [4] to formula [6], and a cyclic aromatic moiety; Formula [1] Formula Π] Formula Π] Pyrazole is either -56- 201132745 [Chemical 5] H2N Ar NH2 1 8 · An amine compound as described in Item (5) of the patent application, wherein the amine compound represented by the formula [1] is a compound represented by the following formula [2]: [Chem. 6] A poly-proline or polyimine obtained by reacting a diamine component comprising a diamine compound according to any one of claims 1 to 18 with a tetracarboxylic dianhydride component. The polyamic acid is obtained by subjecting the polyamic acid to ruthenium iodide. -57- 201132745 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201132745 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none