TW201211108A - Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent which can prevent the occurrence of a whitening phenomenon and a phenomenon of generating a foreign matter on a substrate, enables the production of a liquid crystal alignment film prevented from the reduction in a pretilt angle, and has a good aligning property. Specifically disclosed are: a liquid crystal aligning agent which is characterized by comprising a polyimide that is produced by imidizing a polyamic acid produced by reacting a diamine component with a tetracarboxylic acid dianhydride and a polyol compound that has a tertiary nitrogen atom and a quaternary carbon atom and contains 3 to 15 carbon atoms; a liquid crystal alignment film produced using the composition; and a liquid crystal display element.

Description

[Technical Field] The present invention relates to a liquid crystal aligning agent which suppresses the generation of whitening and foreign matter, and which does not lower the pretilt angle, a liquid crystal alignment film using the same, and a liquid crystal display element. [Prior Art] The liquid crystal display element is a structure in which liquid crystal molecules are sandwiched by a liquid crystal alignment film formed on a substrate, and a display element in which a liquid crystal molecule oriented in a certain direction by a liquid crystal alignment film is responsive to a voltage is used. In the liquid crystal alignment film, a liquid crystal aligning agent (also referred to as a liquid crystal aligning agent) which forms a highly reliable polyimide film is generally used. As a means for forming a polyimide film on a substrate to which an electrode is attached, a coating film of a liquid crystal aligning agent made of a solution of a polyimide precursor such as polylysine is used to make a film on a substrate. A method of amination, and a method of using a solution containing a polyamidimide previously imidized. In the method of using a solution containing a polyimine, a polyimine film having good properties as a liquid crystal alignment film can be formed even at a relatively low temperature firing, but the film formed by the reverse is relatively low in strength. Oriented treatment by rubbing treatment or the like easily causes damage or film peeling to the surface of the film. It is important that the damage or peeling of the surface of the liquid crystal alignment film becomes a cause of display failure when it is a liquid crystal display element. On the other hand, in the method using a solution containing polyimine, polyimine and polylysine are used. In comparison, generally, the solubility in an organic solvent is inferior to that of -5 to 201211108, so that formation of a uniform coating film may become difficult, and it is insoluble in a solvent generally used in a liquid crystal aligning agent, and it is difficult to be contained in a liquid crystal aligning agent. in. Therefore, the solubility of the polyimine contained in the liquid crystal aligning agent is also important. When a liquid crystal aligning agent containing polyimine is used, when printing is performed on a substrate, precipitation is precipitated due to moisture absorption. The quinone imine causes whitening of the varnish and produces a dry surface on the resulting coating film. Further, in the case of a liquid crystal aligning agent containing a polyimide, the adhesion between the polyimide and the printing plate such as APR (Asahi Photosensitive Resin) is also poor, and the printing plate is peeled off during the printing step, and the transfer is directly performed. When the substrate is applied to the substrate, the exfoliated polyimine remains on the substrate as a foreign matter, and these aggregations tend to cause a problem of unevenness in the gap. In the above-mentioned problem, a liquid crystal aligning agent containing a diamine component having a specific structure for improving the friction resistance of the liquid crystal alignment film or the solubility of the polyimine is proposed (see Patent Document 1). Further, there has been proposed a method for suppressing whitening of a varnish containing a polyimine, and a high boiling point solvent capable of suppressing drying time of N-vinylpyrrolidone or N-cyclohexylpyrrolidone by using 50% or more of a solvent (refer to Patent Document 2) * [Provisional Technical Documents] [Patent Document 1] [Patent Document 1] International Publication No. 2006/1 265 5 No. 5 [Patent Document 2] Japanese Patent Laid-Open No. Hei 5 - 1 1 75 87 No. 201211108 The problem to be solved by the invention is not sufficient. For example, in the means of using the solvent having a high boiling point of Patent Document 2, these solvents are generally high in hygroscopicity, so that if the amount of use is increased, The above-described whitening development of the varnish of the liquid crystal aligning agent is increased, and causes a side effect of lowering the pretilt angle of the obtained liquid crystal alignment film. Whitening development in the liquid crystal aligning agent containing the above polyimine, and development of foreign matter on the substrate, and the pretilt angle of the obtained liquid crystal alignment film is lowered. In recent years, the liquid crystal display element has become larger or higher in definition. The demand for quality has become an important issue that must be solved. The present invention provides a liquid crystal aligning agent containing polyimine, which suppresses the whitening development or suppresses the occurrence of foreign matter on the substrate, and suppresses the decrease in the pretilt angle of the obtained liquid crystal alignment film, and the orientation is also good. The liquid crystal aligning agent is for the purpose. Means for Solving the Problems The inventors of the present invention have completed the present invention in order to achieve the above object. That is, the gist of the present invention is as follows. A liquid crystal aligning agent characterized by comprising a polyimine and a polyhydric alcohol compound, wherein the polyamidene is imidized with a polyamine derivative obtained by reacting a diamine component with a tetracarboxylic dianhydride. Further, the polyol compound is a polyol compound having a 3-stage nitrogen atom and a 4-stage carbon atom and having a carbon number of 3 to 15. 201211108 2. The polyol compound is the liquid crystal aligning agent described in the above 1 of the following formula (A). R(?4 5 , Ν-ό-R5 (Α) R1 R3 (wherein R1 and R2 each independently represent a hydroxyalkyl group having 1 to 5 carbon atoms, and R3, R4 and R5 each independently represent a carbon number. The alkyl group of 1 to 5 or the hydroxyalkyl group having 1 to 5 carbon atoms. 3. The polyhydric alcohol compound is a liquid crystal aligning agent described in the above 1 or 2 having 2 to 8 hydroxyl groups. And a liquid crystal aligning agent as described in any one of the above 1 to 3, which is a polyhydric alcohol compound in an amount of 0.1 to 10 parts by mass based on 1 part by mass of the polybenzamine. A liquid crystal aligning agent according to any one of the above 1 to 4, which is a diamino benzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms. 6. The diaminobenzene is the following formula [1] The liquid crystal aligning agent described in the above 5 of the diamine shown. [Chemical 2] h2N NH2

Q / ν Λ = [1] 201211108 7. The diamine component is the liquid crystal aligning agent of the above-mentioned 6 which further contains the diamine represented by the following formula [32]. [Chemical 3]

(in the above formula, k represents an integer of 1 to 20). 8. The liquid crystal orientation described in any one of the above 6 or 7 containing the diamine represented by the formula [1] in the total diamine component: 20 to 90 mol%. Agent. A liquid crystal aligning agent according to any one of the above 7 or 8 wherein the amine of the formula [32] is contained in an amount of from 5 to 40 mol% in the total diamine component. 10. The liquid crystal aligning agent according to any one of the above 1 to 9 is applied onto a substrate on which an electrode is attached, and the obtained liquid crystal alignment film is fired. 1. The liquid crystal display element having the liquid crystal alignment film of the above-mentioned 1 °. The effect of the invention is that the liquid crystal aligning agent of the present invention can suppress whitening or generate foreign matter on a substrate, and agglomerate the foreign matter to cause unevenness in the gap. And a liquid crystal alignment film which suppresses the decrease in the pretilt angle of the obtained liquid crystal alignment film and which is excellent in orientation, and by using the liquid crystal alignment film, the yield can be excellent even in a case of large-scale high-definition Production of highly reliable liquid crystal display elements. The use of the liquid crystal aligning agent of the present invention can suppress whitening development or the development of foreign matter on the substrate by -9-201211108 and the mechanism for suppressing the decrease in the pretilt angle of the obtained liquid crystal alignment film is not clear, but may be considered. For the following reasons. The polyol compound contained in the liquid crystal aligning agent of the present invention is a result of an improvement in solubility of water by a polyimine-containing polymer by forming a salt of a ternary amine having a carboxylic acid group in the polymer. Can improve the tolerance to whitening. Moreover, by the presence of a plurality of hydroxyl groups of the polyol compound, the adhesion between the polymer containing the polyimide and the APR plate is improved, and the generation of foreign matter due to film peeling during printing and the subsequent liquid crystal can be suppressed. The gap of the display element is not uniform. MODE FOR CARRYING OUT THE INVENTION The liquid crystal aligning agent of the present invention contains a polyimine which is a polymer obtained by imidizing a polyamine derivative obtained by reacting a diamine component with a tetracarboxylic dianhydride. . The polyimine used in the present invention is not particularly limited and can be obtained as follows. [Diamine component] The diamine component (may also be referred to simply as a diamine) to be used for obtaining a polyimine is not particularly limited. The diamine may be one or a plurality of species, and the species is not limited. The type of the diamine may, for example, be an alicyclic diamine, an aromatic diamine, a heterocyclic diamine or an aliphatic diamine. This specific example is given below. Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4. '-Diamine-10-201211108--3,3'-dimethyldicyclohexylamine, and isophoronediamine. Examples of the aromatic diamines include fluorene-phenylene diamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-di Aminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 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'-dimethylbiphenylmethyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminopurine, 4,4'-diamino Indole, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diamine Diphenylanthracene, 3,3'-diaminodiphenyl maple, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3 - bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4' -bis(4-aminophenoxy) Benzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy) Phenyl]anthracene, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-bis(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-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoguanidine, 1,3-Diamino hydrazine, 1,6-diamino hydrazine, 1,8-diamino hydrazine, 2,7-diamino hydrazine, -11 - 201211108 1,3-bis(4-amino group Phenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-amine Phenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6·bis(4-aminophenyl) Hexane, 1,7-bis(4-aminobenzene) Heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)decane, 1,10-bis(4-aminophenyl)anthracene Alkane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy) Octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane-1, 3-Diester, bis(4-aminophenyl)butane-1,4-dicarboxylate, bis(4-aminophenyl)pentane-1,5-diester, di(4- Aminophenyl)hexane-1,6-diester, bis(4-aminophenyl)heptane-1,7-diester, bis(4-aminophenyl)octane-1, 8-diester, bis(4-aminophenyl)decane-1,9-diester, bis(4-aminophenyl)decane-1,10-diester, 1,3- Bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4 - (4-Aminophenoxy)phenoxy]pentane, 1,6 - bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8-double [4-(4-Aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]nonane, 1,10-bis[4 -(4-Aminophenoxy)phenoxy]nonane and the like. Examples of the heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2. 7-Diaminodiphenyl-12- 201211108 and furan, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1-azine, 2,5-bis(4-amine Phenyl)-1,3,4-oxadiazole and the like. Examples of the aliphatic diamine include 1,2-diamino1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentanediamine. Alkane, 1,7-diaminoheptane, 1,8-diaminooctane, aminodecane, 1,1 -diaminodecane, 1,3-diamino-2,2- Dimethyl, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dioxane, 1,7-diamino-4,4-dimethyl Heptane, 1,7-diamino-3-methyl, 1,9-diamino-5-methylheptane, 1,12-diaminododecane, amino octadecane, 1, 2-bis(3-aminopropoxy)ethane or the like. In the present invention, as the diamine, a diaminobenzene having a disubstituted amino group substituted with a carbon number of 2 or 3 (hereinafter also referred to as a specific one is preferable. When a specific diamine is used, the solubility of the polymer can be suppressed. The extract is produced. The specific diamine is represented by the following formula [1], and it is preferred to have a disubstituted amino group substituted with a group (hereinafter also referred to as allyl group), 3,5-triethane, I ' 1,6-1,9-diylpropane methylheptyl heptane 1,18-dialkenyl diamine) high and iso-2-propenyl benzene [4]

In the diamine represented by the formula [1], the positions of the respective substituents on the benzene ring are defined, and the positional relationship of the two amine groups is preferably inter- or pairwise. Preferred specific examples of the amines are listed below. No special, the second -13- 201211108 [5]

The formula [2] is 2,4-amino-anthracene, Ν-di-n-propylaniline, and the above formula [3] is 3,5-diamino-anthracene, fluorenyl-diallylaniline, The above formula [4] is 2,5-diamino-indole, fluorenyl-diallylaniline. The diaminobenzene is preferably at least one selected from the group consisting of the above [2], [3] and [4]. Among them, the aforementioned diaminobenzene is particularly preferably 2,4-diamino-indole or fluorenyl-diallyl aniline. In the present invention, the diamine component which is a raw material of the polyimine may be a specific diamine or a combination of a specific diamine and another diamine or two or more kinds thereof. Since the diamine component used for obtaining the polyimine contains a specific diamine, the solubility of the polyimine in an organic solvent can be improved. Moreover, the problem of damage to the film surface or peeling of the film when the coating film is rubbed can be improved. The content of the specific diamine in the diamine component is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 50 mol% or more. The higher the specific diamine content ratio in the diamine component, the higher the effect of suppressing the damage of the surface of the oriented film or the film peeling during the rubbing treatment. Further, the solubility in the organic solvent of the obtained polyimine can also be improved. Further, the diamine component may be only a specific diamine. However, it is preferred to use a diamine other than the specific diamine to impart other characteristics necessary as a liquid crystal alignment film. Therefore, the content of the specific diamine is preferably 90 mol% or less. In particular, when a specific diamine and 4-aminobenzylamine, 3-aminobenzylamine or 4-aminophenethylamine are used, the solubility of the polyimine in an organic solvent becomes high, - 14- 201211108 And a liquid crystal aligning agent which can obtain excellent liquid crystal orientation, the preferred content in the private methylamine, 3-aminobenzylamine, or 4-aminophenyrene is 1 〇mol %~ 50% by mole. Further, in order to increase the pretilt angle of the liquid crystal, a diamine can be used in combination. As the group which can increase the pretilt angle of the liquid crystal, a perfluoroalkyl group, an aromatic cyclic group, an aliphatic cyclic substituent or a steroid skeleton group is preferable. Specific examples of the 1,3-diamine are described below, but are not limited thereto. Further, in the structure shown, j is an integer of 5 to 20, preferably 9 to 17, and preferably an integer of 4 to 15. good. 4-aminophenylbenzene amine component-specific substituent substituent, long-chain alkyl group, combined with these substituents, for the following example, k is 1 to 20, -15- {51 201211108 [6] νη2 Nh2 h2n 八, Y 0(CH2)jCH3 ΝΗ2

[6J η2ν- (CH2)kCH3

(CH2)kCH3 (CH2)kCH3 0(0Η2^0Η3 0(CH2)kCH3 0(CH2)kCH3 n_s^O~nh2 [7] [8] [9] [10] 1111 o=c OiCH^CHs 16- 201211108 [7] h2n

NH〇

-17- s [20) 201211108 [it 8]

0(CH2)kCH3 [21]

[23] [22]

[24] [25] [26]

H2N

[27] -18- 201211108

c; hi1 -19- 201211108 Among the above diamines, the diamines of the formulae [5] and [3 2] are preferred because of their excellent liquid crystal orientation. The diamines of the formulas [12] to [19] are very high in the tilt angle, and are therefore suitable for the alignment film for OCB (Optically Compensated Bend) and the alignment film for VA (Vertical Alignment). Preferred examples of the TN (Twisted Nematic) oriented film (pretilt angle: 3 to 5°) include 5 to 40 mol% of the diamine of the formula [5] or [32] in the diamine component. Preferably, it contains 10 to 30 mol%, and the orientation film (pretilt angle of 1 〇 to 90°) for OCB and VA contains 5 to 60 mol% of the diamine of the formula [12 [19] in the diamine component. Preferably, it is 10 to 40% by mole. Among the above diamines, in particular, the diamine of the formula [3 2] is preferred because it has a high tilt angle and is used in combination with the above specific diamine, even when the friction condition is weak, since the liquid crystal orientation is excellent. Further, as described above, the effect of the diamine to increase the liquid crystal pretilt angle is such that the liquid crystal aligning agent contains a large amount of N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone, which tends to be weakened, and the formula [32] The amine has a characteristic that it is difficult to be affected as such, and it is preferable as a diamine component of the polyimine contained in the liquid crystal aligning agent of the present invention. [Tetracarboxylic dianhydride component] In the present invention, the tetracarboxylic dianhydride component which is a raw material of the polyimine may be one type of tetracarboxylic dianhydride, and two or more types of tetracarboxylic dianhydride may be used. . However, even a polyimine having a high imidization ratio is easy to obtain a relatively high solubility polyimine, and a layer having an alicyclic structure or a layer which can increase the voltage retention of the liquid crystal cell. Aliphatic structure of tetracarboxylic acid-20- 201211108 dianhydride is preferred. Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3. , 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentan tetraresic acid dianhydride, 2,3,4,5-tetrahydrofuran tetraphthalic acid 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, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3, 3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-di -1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.02,5]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, Hexacyclo[6.6.0.3]hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dianhydride, and the like. As a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, particularly, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4 is used. In the case of tetrahydro-1-naphthalene succinic dianhydride or 1,2,3,4-butanetetracarboxylic dianhydride, an oriented film excellent in liquid crystal orientation can be obtained. Further, in addition to the tetracarboxylic acid having an alicyclic structure or an aliphatic structure, when the aromatic tetracarboxylic dianhydride is used, the liquid crystal orientation can be improved and the accumulated charge of the liquid crystal cell can be preferably reduced. Examples of the tetracarboxylic acid tetracarboxylic acid include pyromellitic dianhydride, 3,3,4,4,-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyl. Tetracarboxylic dianhydride, 2,3,3,4-diphenyltetracarboxylic dianhydride, 3,3,4,4,-benzophenone tetracarboxylic dianhydride, 2,3,3 ',4-benzophenone tetraresole-21 - 201211108 Acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like. As an aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether A dianhydride or a 1,4,5,8-naphthalenetetracarboxylic dianhydride is particularly preferred. Considering the balance of solubility of polyimine, orientation of liquid crystal, and voltage retention rate 'accumulated charge, tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, and aromatic tetracarboxylic acid Among the ratios of the anhydrides, the former has a molar ratio of 90/10 to 50/50, preferably 80/20 to 60/40. [Polyimide and the method for producing the same] The polyimine used in the liquid crystal aligning agent of the present invention is an aminated group which is obtained by reacting the polyamine of the diamine component and the tetracarboxylic dianhydride component. Yttrium. Among them, polylysine is obtained by mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent and reacting them. The method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent is a solution in which a diamine component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component is directly added, or a dispersion or Method of adding after dissolving in an organic solvent. Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, etc. . Further, when the tetracarboxylic acid di-fraction component or the diamine component is formed of a plurality of compounds, the polymerization may be carried out in a state in which a plurality of components of these -22-201211108 are mixed in advance, or the polymerization may be carried out in sequence. The temperature at which the tetracarboxylic dianhydride component and the diamine component are polymerized in an organic solvent is usually 〇 150 ° C, preferably 5 to 100 ° C, more preferably 10 ° C to 80 ° C. When the temperature is high, the polymerization reaction can be increased, but if it is too high, a polymer having a high molecular weight cannot be obtained. Further, the polymerization reaction can be carried out at any concentration. However, the lower the concentration, the more difficult it is to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high, and it is difficult to uniformly stir the tetracarboxylic dianhydride. The total concentration of the component and the diamine component is preferably from 1 to 50% by mass, preferably from 5 to 30% by mass. The initial stage of the polymerization reaction is carried out at a high concentration, and thereafter an organic solvent may be added. The organic solvent to be used in the above reaction is not particularly limited as long as it can dissolve the produced polyamic acid, and N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone or the like can also be used. Solvent. To cite such a specific example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam , dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, trimethylamine hexamethyl phosphate, γ-butyrolactone, 1,3-dimethylimidazolidinone and the like. These can be used alone or in combination. Further, it may be a solvent in which polylysine is not dissolved, and may be used in combination with the above solvent in the range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes the polyamic acid formed by the hydrolysis, it is preferred that the organic solvent be desalted as much as possible. The molar ratio of the tetracarboxylic dianhydride component to the di-23-201211108 amine component used in the polymerization of polylysine is preferably 1:0.8~1:1.2, and the molar ratio is closer to 1: At 1 o'clock, the molecular weight of the resulting polyamic acid is greater. The molecular weight of the polyimine obtained by imidization can be adjusted by controlling the molecular weight of the polyamine. The molecular weight of the polyimine contained in the liquid crystal aligning agent of the present invention is not particularly limited, but the weight average molecular weight is preferably 2,000 to 200,000, more preferably from the viewpoint of the strength of the coating film and the ease of handling as a liquid crystal aligning agent. It is 5,000~50,000. As described above, the imidization of the obtained polyglycolic acid can be carried out in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 100 hours. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity for carrying out the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Further, since the imidization of acetic anhydride is completed, the purification of the obtained polyimine can be easily carried out, which is preferable. As the organic solvent, the solvent used in the polymerization of the above polyamic acid can be used. The imidization ratio of the polyimine can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The amount of the alkaline catalyst at this time is preferably 0.2 to 10 times the molar amount of the proline group of the polyamic acid of the raw material, more preferably ~. 5 to 5 times the molar. Further, the amount of the acid anhydride is preferably from 1 to 30 moles per mole of the proline group of the polyamic acid of the starting material, more preferably from 1 to 1 mole. The reaction temperature is preferably -20 to 250 ° C, more preferably 0 to 180 ° C. The imidization ratio of the polyimine contained in the liquid crystal aligning agent of the present invention is not particularly limited. However, in consideration of electrical characteristics, it is preferably 40% or more, and it is desired to obtain a high voltage holding ratio from -24 to 201211108. More than 60% is better, better. In the solution of the polyimine thus obtained, it is preferred to use the present invention after recovering and washing the polyimide. The polyimine is recovered by dissolving the polyamidene in a poor solvent which is imidized and then filtered. The agent may, for example, be methanol, acetone, hexane, butyl acetophenone, methyl isobutyl ketone, ethanol, toluene or benzene. The washing of the amine can also be carried out in the poor solvent. The polyimine thus recovered and washed becomes a powder after normal pressure or temperature or heat drying. [Polyol Compound having Grade 3 Nitrogen and Grade 4 Carbon] The liquid crystal aligning agent of the present invention contains a ternary alcohol compound. When the polyol compound has 3 and does not have both of them, the degree of the above-described inability to achieve the present invention is small. For example, the hydroxyl group and the third-order nitrogen atom shown in the comparative examples described later do not have the above-described four-stage carbon atom, and the above object of the present invention is not attained. The total carbon number of the polyol compound must be from 3 to 13, more preferably from 6 to 12. The polyol compound preferably has 2 to 8 hydroxyl groups, more preferably 2 to 7 hydroxyl groups. When the hydroxyl group is too large, the display characteristics of the liquid crystal display element are more than 80%, and the added liquid crystal orientation is added. The agent liquid is put into the polycondensate, the heptane, and the methyl group recovered under the decompression of the polycondensate, and the nitrogen and the fourth grade carbon of the nitrogen and the fourth grade carbon, the purpose, or the achievement Even in the case of having a plurality of triethanolamines 3 to 15 , it is preferred that the number of hydroxyl groups of f is particularly preferably 2 to 5, and conversely, if the number of -25 to 201211108 is too small, the adhesion to the APR version is Sex will be worse. The number of the three-stage nitrogen atom and the four-stage carbon atom may be one or more, and preferably five or less, and more preferably three or less. Further, the polyol compound preferably has an aliphatic saturated hydrocarbon structure, and when the total carbon number is large, it may have an unsaturated bond in one part and a cyclic structure in a part. The polyol compound is preferably a compound represented by the following formula (A). [it 1〇] (A)

VP R1 R3 In the above formula (A), R^R2 each independently represents a hydroxyalkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and R3, R4 and R5 each independently represent a carbon number of 1 to 5, preferably An alkyl group of 1 to 3, or a hydroxyalkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Preferred examples of the compound represented by the formula (A) include the following compounds. -26- 201211108 [Chem. 11]

HO

HO

HO

OH

OH

HO

OH

OH

OH

OH

HO

OH

HO

OH

OH

OH

[Liquid Crystal Orienting Agent] The liquid crystal aligning agent of the present invention contains the polyimine as a polymer component, and a polyol compound having a third-order nitrogen and a fourth-order carbon as an additive component, and these are dissolved in a solvent. The content of the polyol compound of the polyimine in the liquid crystal aligning agent is preferably 0.1 to 10 parts by mass in terms of 201211108, and preferably 0.5 to 5 parts by mass, based on 1 part by mass of the polyimine. When the polyol compound is excessively contained, the properties of the obtained liquid crystal display element are deteriorated. Conversely, if the amount is too small, the effect of the present invention is small. The content (concentration) of the polyimine in the liquid crystal aligning agent can be appropriately changed depending on the setting of the thickness of the liquid crystal alignment film to be formed, but it is preferably 9 to 99 parts by mass for 1 part by mass of the polyimine. More preferably, it is suitable for 1 to 1.5 parts by mass. When the amount of the solvent is more than 99 parts by mass, it becomes difficult to form a uniform and defect-free coating film. Conversely, if it is less than 9 parts by mass, the storage stability of the solution may be deteriorated. Further, the content of the solvent in the liquid crystal aligning agent of the present invention is preferably from 90 to 99% by mass, more preferably from 92 to 98 parts by mass, based on the entire liquid crystal aligning agent. The solvent used for the liquid crystal aligning agent of the present invention may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or N-methyl. Caprolactam, 2-pyrrolidone, N-vinylpyrrolidone, dimethyl submilling, tetramethylurea, dimethylhydrazine, hexamethylarylene, butyrolactone, 1,3-dimethyl-imidazole Alkanone and the like. Among them, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, and γ-butyrolactone are preferred because of their high solubility in polyimine. Further, r-butyrolactone can be used to inhibit whitening. In addition, when the solvent used for the liquid crystal aligning agent of the present invention contains N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone, it is possible to suppress whitening of the coating film or uneven film thickness in the vicinity of the printing edge. Better. When the amount of the solvent is 0.5 parts by mass or more based on 1 part by mass of the polymer, an effect of suppressing the generation of aggregates can be obtained, and it is preferably from 1 to 80 parts by weight, more preferably from 2 to 70 parts by weight. -28- 201211108 The polyimine contained in the liquid crystal aligning agent of the present invention may be a mixture of two or more kinds of polyimines having different structures, and may not deteriorate the storage stability of the varnish without impairing electrical properties. At the same time as the agglomerate which causes the gap unevenness of the liquid crystal screen to be produced at the time of printing, polylysine or other polymer can be used. The amount of the polymer to be used is preferably 0.05 to 7 parts by mass, more preferably 0.1 to 4 parts by mass, per part by mass of the polyimide. The content of the polyimine-containing polymer in the liquid crystal aligning agent of the present invention is preferably from 1 to 10% by mass, preferably from 2 to 8% by mass based on the total of the liquid crystal aligning agent. The solvent used in the liquid crystal aligning agent of the present invention may also partially contain a solvent having a low surface tension. By mixing the solvent component with a moderate solvent having a low surface tension, the uniformity of the coating film when the substrate is applied can be improved. As a solvent having a low surface tension, ethyl celecoxib, butyl siroli, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1- Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, diethylene glycol diethyl ether, propylene glycol Monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol _ 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-( 2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. Among them, from the viewpoint of coatability to the substrate, it is particularly preferable to use butyl sirolimus, ethyl carbitol, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether. A solvent having a low surface tension can improve the coating property on a substrate. However, when the amount is too large, precipitation of a polymer occurs, so that the content is preferably 60% by mass or less based on the solvent component. Preferably, it is 50% by mass or less. When a solvent which has a solubility in a resin component and a solvent having a low surface tension are used, a solvent having a low surface tension in a solvent having a solubility in the resin component of 5 to 70% by mass in a preferable content of each solvent is preferable. The solvent is 10 to 60% by mass, more preferably 10 to 45% by mass for ensuring the solubility of the resin component, and 20 to 50% by mass of the solvent having a low surface tension. The liquid crystal aligning agent of the present invention may, for example, be 3-aminopropylmethyldiethoxydecane, 3-phenylaminopropyltrimethoxydecane or 3-aminopropyltriethoxydecane, A decane coupling agent such as aminoethylaminomethylmethyl)phenethyltrimethoxydecane. By the addition of these decane coupling agents, the adhesion to the coating film of the substrate can be further improved. The content of the decane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per part by mass of the polymer. [Preparation method of the liquid crystal aligning agent] The method of preparing the liquid crystal aligning agent of the present invention is not particularly limited as long as the respective components mainly composed of the polyimine are in a uniform state in the liquid crystal aligning agent. To cite one example, a powder of polyimine is dissolved in a solvent as a polyimine solution, followed by a solvent to a desired concentration and diluted. In the dilution step, adjustment of the solvent composition for controlling the coating property to the substrate, addition of an additive for improving the coating film property, and the like can be performed. It is preferred that the liquid crystal aligning agent obtained as described above is applied to the substrate for filtration. -30-201211108 The liquid crystal aligning agent of the present invention can be applied to a substrate by drying and baking, and the surface of the coating film can be rubbed to obtain a liquid crystal alignment film for rubbing. Further, it may be used as a liquid crystal alignment film for VA or a light alignment film instead of the 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 an I which can be driven by a liquid crystal can be used. In the case of a substrate such as a TO electrode, it is preferable from the viewpoint of simplification of the step. Further, in the reflective liquid crystal display device, not only a single-sided substrate but also an opaque substance such as a germanium wafer may be used, and in this case, a material which can reflect light such as metal aluminum or the like may be used as a liquid crystal alignment agent. The rolling coating method, the printing method, the inkjet method, and the like are mentioned, but industrially, the relief printing method is widely used from the viewpoint of productivity, and is also applicable to the liquid crystal aligning agent of the present invention. Although the drying step after the application of the liquid crystal aligning agent is not essential, the drying step is preferably carried out when the time from the application to the baking is not constant for each substrate, or when the baking is not performed immediately after the application. This drying is not required to evaporate the solvent to the extent that the shape of the coating film is deformed by the conveyance of the substrate or the like, and the drying means is not particularly limited. To cite a specific example, a drying method of preferably 50 to 150 ° C, preferably 80 to 120 ° C, for 0.5 to 30 minutes, more preferably 1 to 5 minutes, is used. The baking of the substrate coated with the liquid crystal aligning agent can be carried out at any temperature of 10 〇 to 3 5 CTC, but preferably 15 (TC 30 30 CTC, more preferably 180 ° C to 250 ° C. In the liquid crystal aligning agent) When a proline group is present, the calcination temperature is changed from -31 - 201211108 proline to imidization, but it is not necessary to make it 100% iminolated at this time. When the thickness is too thick, it is disadvantageous in the level of power consumption of the liquid crystal display element. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 10 to 200 nm, more preferably 50 to 100 nm. As the rubbing treatment of the coating film surface formed on the substrate, an existing friction device can be used. Examples of the material of the rubbing cloth at this time include cotton, rayon, nylon, etc. The liquid crystal display element of the present invention is used. In the above method, a liquid crystal alignment cell is obtained by a known method, and a liquid crystal cell is produced by a known method. The liquid crystal cell is used as a liquid crystal display element. 1 pair of substrates, preferably 1~3 0μιη, The spacer of 2~10μιη is set to any angle of 0 to 270°, and the surrounding is fixed by a sealant, and the method of sealing after injecting liquid crystal is general. The method for sealing the liquid crystal is not particularly limited, and the method is prepared. After the liquid crystal is decompressed in the liquid crystal, a vacuum method in which a liquid crystal is injected, a dropping method in which a liquid crystal is dropped, and a sealing method can be exemplified. The liquid crystal display element thus obtained can be applied to a liquid crystal display element, an STN liquid crystal display element, or a TFT liquid crystal display. The element and the OCB liquid crystal display element are more applicable to a display element such as a liquid crystal display element of a planar electric field switching type or a VA liquid crystal display element. [Embodiment] [Embodiment] -32 - 201211108 Hereinafter, an embodiment will be described. The present invention will be described in detail, but the present invention is not limited thereto. The abbreviations used in the examples and comparative examples are as follows: <tetracarboxylic dianhydride> A-1 : 1,2,3,4 - cyclobutane tetracarboxylic dianhydride A-2 : pyromellitic dianhydride <diamine> B-1 : 2,4-diamino-N,N-diallylaniline [Chemical 12]

B-2: 3-aminobenzylamine B-3: 4-(trans-4-pentylcyclohexyl)benzoguanamine-2',4'-phenylenediamine [Chemical 13]

B_4: 4-tetradecyloxy-1,3-diaminobenzene <Additive> -33- 201211108 Compound-1: bis(2-hydroxyethyl)aminoglycol (hydroxymethyl)methane 14]

Compound-2: N-tert-butyldiethanolamine [it 15]

H3c-^, ch3 ch3 compound-3: triethanolamine [Chemical 16]

Compound-4: propylamine [it 17]

H3c -34- 201211108 <Organic solvent> NMP: N-methyl-2-pyrrolidone NEP : N-ethyl-2-pyrrolidone GBL : γ-butyrolactone DMI : 1,3-dimethylimidazolidinone BS : butyl siroliol <Measurement of molecular weight> The molecular weight of polyimine was determined by GPC (normal temperature gel permeation chromatography) apparatus to calculate polyethylene glycol and poly The number average molecular weight and weight average molecular weight of the oxime converted by ethylene oxide. GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: made by Shodex (inline of KD803, KD805)

Column temperature: 50 °C Dissolution: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr'H2〇) is 30 mmol/l, phosphoric acid. Anhydrous crystal (〇·phosphoric acid) is 30 mmol/l, tetrahydrofuran (THF) 10 ml/l) Flow rate: 1.0 ml/min calibration line Standard sample: TSK standard polyethylene oxide manufactured by TOSOH Co., Ltd. (weight average molecular weight about 900,000, 15 〇) , 〇〇〇, 1 00,000 ' 3 0,000 ), and Polyethylene glycol (weight average molecular weight of about 1,200, 4,000, 1, 〇〇〇) manufactured by Polymer Laboratory. <Measurement of imidization ratio> -35- 201211108 The imidization ratio of polyimine was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube, and a hydrogenated dimethyl submill (DMSO-d6 > 0.05% TMS mixture) of 0.5 3 m 1 was added to completely dissolve it. This solution was measured for proton NMR at 500 MHz using a NMR measuring instrument (JNM-ECA500) manufactured by JEOL Ltd. The imidization ratio is determined by a proton derived from a structure which does not change before and after imidization as a reference proton, and the peak of the proton is used to calculate 値 and an NH group derived from proline which is present in the vicinity of 9.5 to 10.0 ppm. The proton peaks are calculated by the following formula. Iminoation rate (%) = (l-a_x/y) χΙΟΟ In the above formula, x is the proton peak product 値 from the NH group of proline, y is the peak product of the reference proton, α, α is polyamine The ratio of the number of reference protons of a proline to one ruthenium matrix in the case of an acid (imidization ratio of 0%). (Example 1) As the tetracarboxylic dianhydride component, 13-53 g (0.069 mol) of hydrazine-1 and 6.54 g (0.030 mol) of A-2 are used, and as the diamine component, 6.1 g of B-1 is used. 0.03 0 mol ) , 4.8 9 g ( 0.0 4 0 m ο 1 ) of B-2, 9.62 g (0-30 mol) of B -4, and obtained a polyamine acid solution after reacting for 24 hours at room temperature in NMP 162.7 g. * In 142.8 g of the polyamic acid solution, NMP 255.64 g was added and diluted to -36-201211108, and 20.64 g of acetic anhydride and 8.8 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize it. . After the reaction solution was cooled to room temperature, it was poured into 1498.8 ml of methanol, and the precipitated solid was collected. Further, the solid was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of polyimine (SPI-1). The polyimine had a number average molecular weight of 13,653 and a weight average molecular weight of 33,847. Further, the imidization ratio was 90%. After 5 g of GBL was added to 5 g of the obtained polyimine SPI-1 powder to completely dissolve it, 30 g of BS was added thereto, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the time of the end of the agitation, the polyimine was completely dissolved. After returning to room temperature, 25.25 g of Compound-1 was added, and after stirring for 3 hours, a liquid crystal aligning agent was obtained. (Example 2) After adding 65 g of NMP to 5 g of the polyimine SPI-1 powder and completely dissolving it, 30 g of B S was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. The polyimine was completely dissolved at the end of the agitation. After returning to room temperature, 0.25 g of Compound-1 was added, and after stirring for 3 hours, a liquid crystal aligning agent was obtained. (Example 3) After 5 g of NEP(R) was added to 5 g of the polyimine SPI-1 powder to completely dissolve it, 30 g of BS was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours • 37 - 201211108. The polyimine was completely dissolved at the end of the agitation. After returning to room temperature, 〇·25 g of Compound-1 was added, and after stirring for 3 hours, a liquid crystal directing agent was obtained. (Example 4) As the tetradecanoic dianhydride component, 8.18 g (42 mmol) of A-1 and 1.63 g (7.5 mmol) of A-2 were used, and as the diamine component, 1.2 2 g of B-2 was used (1). Ommol), B -1 5 . Ο 8 g ( 2 5 mm ο 1 ), 6.13 g (15 mmol) of B - 3 , NMP 88.96 g, reacted at room temperature for 24 hours to obtain a poly-proline solution. . To 95.8 g of the polyamic acid solution, 228.5 g of NMP was added and diluted, and 15.1 g of acetic anhydride and 6.4 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize. The reaction solution was cooled to room temperature, and then poured into 1259.1 ml of methanol to recover the precipitated solid. Further, the solid was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of soluble polyimine (SPI-2). The polyimine had a number average molecular weight of 18,195 and a weight average molecular weight of 57,063. Further, the imidization ratio was 93%. After adding 65 g of GBL to 5 g of the obtained polyimine SPI·2 powder and completely dissolving it, 3 〇g of BS ' was added and stirred at a temperature of 5 ° C for 24 hours. The polyimine was completely dissolved at the end of the agitation. After returning to room temperature, 25.25 g of Compound-1 was added, and after stirring for 3 hours, a liquid crystal aligning agent was obtained. -38-201211108 (Example 5) After adding 65 g of NMP to 5 g of the polyimine SPI-2 powder and completely dissolving it, 30 g of BS was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. The polyimine was completely dissolved at the end of the agitation. After returning to room temperature, 2. 2 5 g of Compound-1 was added, and after stirring for 3 hours, a liquid crystal aligning agent was obtained. (Example 6) After adding 65 g of NEP to 5 g of the polyimide SPI-2 powder to completely dissolve it, 30 g of BS was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. The polyimine was completely dissolved at the end of the agitation. After returning to room temperature, 〇·25 g of Compound-1 was added, and after stirring for 3 hours, a liquid crystal aligning agent was obtained. (Example 7) After adding 65 g of GBL to 5 g of the polyimine SPI-1 powder to completely dissolve it, 30 g of BS was added at a temperature of 50. (: stirring was carried out for 24 hours. At the end of the stirring, the polyimine was completely dissolved. After returning to room temperature, '0 2 2 g of the compound-2 was added and stirred for 3 hours. (Example 8) After adding 65 g of NMP to 5 g of the imine SPI-1 powder and completely dissolving it, 30 g of BS was added at a temperature of 50. (: stirring was carried out for 24 hours. At the end of the stirring, the polyimine was completely dissolved. After returning to room-39-201211108, 0.25 g of Compound-2 was added and stirred for 3 hours. (Comparative Example 1) After adding 65 g of GBL to 5 g of the polyimide SPI-1 powder, it was completely dissolved. 30 g of BS was added, and a liquid crystal aligning agent was obtained after stirring for 24 hours at a temperature of 50 ° C. The polyimine was completely dissolved at the end of the stirring (Comparative Example 2) 65 g of 5 g of the polyimide SPI-1 powder was added. After NMP was completely dissolved, 30 g of BS was added, and a liquid crystal aligning agent was obtained after stirring at 50 ° C for 24 hours, and the polyimine was completely dissolved at the end of the stirring. (Comparative Example 3) In the polymerization Add 65g of NEP to 5g of quinone imine SPI-1 powder, and after it is completely dissolved, add 30g of BS at temperature 5 The liquid crystal aligning agent was obtained by stirring at 0 ° C for 24 hours, and the polyimine was completely dissolved at the end of the stirring. (Comparative Example 4) After adding 65 g of GBL to 5 g of the polyimide SPI-1 powder to completely dissolve it, After adding 30 g of BS and stirring at a temperature of 50 ° C for 24 hours, a liquid crystal aligning agent was obtained. At the end of the stirring, the polyimine -40 - 201211108 was completely dissolved. After returning to room temperature, 0.25 g of the compound-3 was added. After stirring for 3 hours, a liquid crystal aligning agent was obtained. (Comparative Example 5) After adding 65 g of NMP to 5 g of the polyimide SPI-1 powder and completely dissolving it, 30 g of BS was added, and the temperature was 50 ° C. Stirred for an hour. At the end of the stirring, the polyimine was completely dissolved. After returning to room temperature, 0.25 g of Compound-3 was added and stirred for 3 hours. (Comparative Example 6) Polyimine SPI-2 powder After adding 65 g of GBL to 5 g and completely dissolving it, 30 g of BS was added, and a liquid crystal aligning agent was obtained at a temperature of 5 (TC was stirred for 24 hours. At the end of the stirring, the polyimine was completely dissolved. (Comparative Example 7) Add 65g of NEP to 5g of polyamidamine SPI-2 powder to completely dissolve it 30 g of BS was added, and the liquid crystal aligning agent was obtained after stirring at a temperature of 5 Torr for 24 hours. At the end of the stirring, the polyimine was completely dissolved (Comparative Example 8) 65 g of the polyimine SPI-2 powder was added to 5 g. After GBL was completely dissolved, 30 g of BS was added and stirred at a temperature of 5 (TC for 24 hours - 41 - 201211108). The polyimine was completely dissolved at the end of the agitation. After returning to room temperature, 0.25 g of Compound-4 was added and stirred for 3 hours to obtain a liquid crystal directing agent. With respect to the liquid crystal aligning agents of Examples 1 to 8 and Comparative Examples 1 to 8 obtained above, the measurement of the inclination angle, the evaluation of the whitening characteristics, and the evaluation of the foreign matter at the time of printing were carried out as follows. The results are shown in Tables 1 and 2. <Measurement of pretilt angle> The liquid crystal aligning agent was subjected to roll coating on a glass substrate with a transparent electrode, and dried at 70 (heating of TC for 70 seconds, and then at 21 (TC of hot plate) The film was fired for 10 minutes to form a coating film having a film thickness of 100 nm. The surface of the coating film was rayon cloth having a roll diameter of 12 mm, and the number of rolls was rotated by 1000 rpm, the speed of the roll was 50 mm/Sec, and the amount of press-in was 0. Rubbing was carried out under conditions of 3 mm to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate were prepared, and a spacer of 6 μm was spread on the surface of the liquid crystal alignment film, and the sealant was applied from the top to the other. After the sheet substrate is straightened in the rubbing direction facing the liquid crystal alignment film surface, the sealing agent is hardened to produce a hollow cell. The liquid cell is injected into the liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) by a vacuum injection method, and the film is sealed. The twisted nematic liquid crystal cell was obtained after the injection. The liquid crystal cell obtained by the above method was used for the measurement of the pretilt angle. The measurement was carried out using TBA107® manufactured by Autronic Co., Ltd. <Evaluation of whitening characteristics> -42-201211108 , in Cr base About 0.1 ml of each was dropped, and it was placed in an environment of a temperature of 23 ° C and a humidity of 7 〇 %. The end of the droplet was observed near the center and near the center by microscopic observation every hour, and the end of the droplet was nearly 1 〇. 〇 times, observed at a magnification of 50 times near the center of the droplets. When the agglomerates were observed at the end and the center of the droplets within 6 hours, it was evaluated as X, and it was evaluated as 〇 even after 6 hours. When the agglomerate was slightly observed at the end of the droplet within 6 hours, it was evaluated as Δ. The results are shown in Table 2. <Evaluation of foreign matter at the time of printing> The printing was carried out using the same apparatus as described above. Thereafter, the printing machine was stopped for 1 minute, and the printing plate was dried. Thereafter, one piece of the Cr substrate was printed and fired in the same manner as above. The fired substrate was observed by a confocal laser microscope (trade name: VL2000, manufactured by Lasertec). In the vicinity of the printing edge, those who did not produce foreign matter near the edge of the printing were evaluated as 〇'. The foreign matter that produced 0.1~3μιη was evaluated as △, and the foreign matter that produced 3μιη or more was evaluated as X. The results are shown in Table 2» -43- 201211108 [Table 1 Polymeric anhydride Diamine Amine Addition Imidation Rate Solvent Composition Example 1 SPI-1 A—I, A-2 B_1 B-2 B-4 Chemical-1 90 GBL(65). BS(30) Example 2 SPI -1 A-1. A-2 B-1 Β-2 Β-4 Compound-1 90 NMPI65), BS(30) Example 3 SPI-I A-1. A-2 Β-1 Β-2 Β- 4 Compound-1 90 NEP(65), BSI30) Example 4 SPI-2 Al. A-2 Β-Ι Β-2 Β-3 Compound-1 93 GBL (65). BS(30) Example 5 SPI- 2 AI. A-2 Β-1 Β-2 Β-3 Compound-1 93 NMP(65). BS(30) Example 6 SPI-2 A-1, A-2 Β-1 Β-2 Β-3 Compound-1 93 NEP(65). BS(30) Example 7 SPI-1 Al, A-2 Β-1 Β_2 Β~4 Compound-2 90 GBL (65). BS(30) Example 8 SPI-1 A-1, A-2 Β-1 Β-2 Β-4 Compound-2 90 NMP(65), BS(30) Comparative Example 1 SP1-1 AI, A-2 Β-1 Β-2 Β-4 m 90 GBL (65). BS(30) Comparative Example 2 SPI-1 Al. A-2 Β-1 β-2 Β-4 Ant. Nor 90 NMP(65), BS(30) Comparative Example 3 SPI-1 A —l, A-2 Β~1 Β-2 Β-4 «ΑτΓ m 90 NEFI65). BS(30) Comparative Example 4 SPI-I Al. A-2 Β-1 Β-2 Β-4 Compound-3 90 GBL (65). BS(30) Comparative Example 5 SPI-1 A— 1. A-2 ΒΊ Β~2 Β~4 Compound-3 90 NMP(65). BS(30) Comparison Example 6 SPI-2 Al, A-2 Β-1 Β-2 Β-3 No 93 GBL (65). BSI30) Comparative Example 7 SPI-2 A-Ι. A-2 Β-1 Β-2 Β-3 No 93 N£P(65). BS(30) Comparative Example 8 SPI-2 Al. A-2 Β-1 Β-2 Β-3 Compound-4 93 GBL (65). BS(30) [Table 2]

Polymer Additive Pretilt Whitening Foreign Body Example 1 SPI-1 Compound-1 3. 1 〇〇 Example 2 SPI-1 Compound-1 3. 1 〇〇 Example 3 SPI-1 Compound-1 3. 1 〇〇 Example 4 SPI-2 Compound-1 6. 8 〇〇 Example 5 SPI-2 Compound-1 6.7 〇〇 Example 6 SPI-2 Compound-1 6. 7 〇〇 Example 7 SPI-1 Compound-2 3 1 〇Δ Example 8 SPI-1 Compound-2 3. 1 〇〇Comparative Example 1 SPI-1 jfnr m 3. 0 Δ X Comparative Example 2 SPI-1 m 2.3 (0.7) X Δ Comparative Example 3 SPI-1 4rrf. m 2. 2 (0. 8) Δ Δ Comparative Example 4 SPI-1 Compound-3 3. 1 〇X Comparative Example 5 SPI-1 Compound-3 2. 7 (0.44) 〇Δ Comparative Example 6 SPI -2 fnT- pick 6.7 XX Comparative Example 7 SPI-2 «fjrrp 5.4 (1.3) X Δ Comparative Example 8 SPI-2 Compound-4 6.7 XX The parentheses in the table indicate the pre-week when compared with the GBL main solvent system. The dip is reduced. -44-201211108 Industrial Applicability The liquid crystal produced by using the liquid crystal aligning agent of the present invention is a highly reliable liquid crystal display device, and is applicable to display of various modes such as TN, STN liquid crystal display elements, TFT liquid crystal display elements, and elements. element. Display component can be liquid crystal display element OCB liquid crystal display -45-

Claims (1)

201211108 VII. Patent application scope: 1. A liquid crystal aligning agent characterized by containing a polyimine and a polyol compound, wherein the polyimine is a polyamine obtained by reacting a diamine component with a tetracarboxylic dianhydride. The polyamidimide obtained by imidization of an acid is a polyol compound having a 3-stage nitrogen atom and a 4-stage carbon atom and having a carbon number of 3 to 15. 2. The liquid crystal aligning agent according to claim 1, wherein the polyol compound is represented by the following formula (A); [Chemical Formula 1] %-C-R5 (A) R1 R3 (wherein R1) R2 each independently represents a hydroxyalkyl group having 1 to 5 carbon atoms, and R3, R4 and RS each independently represent an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms. 3. A liquid crystal aligning agent according to claim 1 or 2, wherein the polyol compound is a compound having 2 to 8 hydroxyl groups. 4. The liquid crystal directional agent according to any one of items 1 to 3 of the patent application wherein the polyol compound is any one of the following compounds; -46- 201211108 [Chemical 2] HO HO HO OH OH OH OH OH OH OH HO OH HO OH OH OH 5. The liquid crystal director according to any one of claims 1 to 4, wherein 0.1 to 10 parts by mass of the polyol compound is contained per 1 part by weight of the polyimine. 6. The liquid crystal 201211108 agent according to any one of claims 1 to 5, wherein the diamine component is a diamine group having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms. benzene. 7. The liquid crystal aligning agent according to claim 6, wherein the diaminobenzene is a diamine represented by the following formula [1]; [Chemical 3] h2n NkU 8. The liquid crystal aligning agent according to claim 7, wherein the diamine component further contains a diamine represented by the following formula [32]; (In the above formula, k represents an integer of 1 to 20). 9. The liquid crystal aligning agent according to item 7 or item 8 of the patent application, which contains 20 to 90 mol% of the diamine of the formula [1] in the total diamine component. The liquid crystal aligning agent of claim 8 or claim 9, which further contains 5 to 40 mol% of the diamine of the formula [32] in the total diamine component. 11. The liquid crystal aligning agent according to any one of the items 1 to 10, wherein the content of the polyimine-containing polymer is from 1 to 1% by mass in the liquid crystal aligning agent containing a solvent. . 201211108 1 2 . A liquid crystal alignment film, which is characterized in that a liquid crystal aligning agent according to any one of the first to eleventh aspects of the patent application is applied to an electrode-attached substrate and is fired. Winner. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 12 of the patent application. -49- 201211108 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: no-3-v 201211108 V. If there is a chemical formula in this case, please reveal the best Chemical formula showing the characteristics of the invention: none