TWI586639B - Diamine, polymer, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to novel diamines, polyimine precursors, polyimine and polyamines, liquid crystal alignment agents, and liquid crystal alignment films, and to liquid crystal display elements.

Among the liquid crystal display elements, the liquid crystal alignment film serves as a function of aligning the liquid crystal in a certain direction. Nowadays, the main liquid crystal alignment film used in the industry is formed by a solution of polyamic acid (also known as PAA), polyamidomate or polyimine. The polyimine-based liquid crystal alignment agent is applied to a substrate to form a film. Further, when the liquid crystal is horizontally aligned, parallel-aligned, or obliquely aligned with respect to the substrate surface, a surface extension treatment by rubbing is performed after the film formation. In addition, as a method of replacing the rubbing treatment, a method of using an anisotropic photochemical reaction such as polarized ultraviolet light has been proposed, and in recent years, it has been reviewed for industrialization.

In order to enhance the display characteristics of such a liquid crystal display element, the structure of polylysine, polyphthalate or polyimine is changed by a method such as polyglycine, which has different blending characteristics, and poly Glutamine or poly The imine or the like, or an additive or the like, for improving the liquid crystal alignment property, electrical properties, etc., and controlling the pretilt angle. For example, it has been proposed to use a polymer which has a specific structure as a side chain (refer to Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2001-517719

However, as the performance of the liquid crystal display element is increased, the area is increased, and the power consumption of the display device is progressing, the characteristics required for the liquid crystal alignment film are becoming more and more severe. When a conventional liquid crystal alignment agent such as Patent Document 1 is used, The burn-in characteristics are insufficient, and the liquid crystal alignment performance changes due to AC (alternating current) driving, resulting in image sticking, which still has problems.

An object of the present invention is to solve the above problems of the prior art, and to reduce a change in liquid crystal alignment performance of a liquid crystal alignment film driven by an AC, and to provide a liquid crystal display element having excellent afterimage characteristics. That is, it is intended to provide a novel diamine which can obtain a liquid crystal alignment film having a polyimine precursor, a polyimine or a polyamine, and the liquid crystal alignment film is a liquid crystal display element having the above-described characteristics. Further, it is intended to provide a liquid crystal alignment agent and a liquid crystal display element using the diamine.

As a result of intensive studies, the present inventors have found a liquid crystal alignment agent comprising a polyimine precursor, a polyimine or a polyamine which uses a specific diamine represented by the following formula (1) as a diamine component. It is extremely effective to achieve the above object, and the present invention has been completed. Further, the diamine represented by the following formula (1) is a novel compound not described in the literature.

That is, the present invention has the following gist.

A diamine characterized by the following formula (1), (In the formula (1), X ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms (however, the non-adjacent -CH ₂ - of the alkylene group may be bonded via an ether bond, an ester bond or a guanamine bond) Substituting), X ² is -OCO-CH=CH- or -CH=CH-COO-, X ³ is a single bond, an alkylene group having a carbon number of 1 to 10 or a divalent benzene ring, and X ⁴ is a single bond, - OCO-CH=CH- or -CH=CH-COO-, X ⁵ is a single bond or an alkylene group having 1 to 6 carbon atoms (however, the non-adjacent -CH ₂ - of the alkylene group may be ether-bonded) The ester bond or the guanamine bond is substituted; however, the formula (1) has one or more cinnamyl groups).

A polymer selected from the group consisting of a polyimine precursor obtained by using the above-mentioned diamine, a polyimine obtained by imidating the polyimine precursor ruthenium, and a poly At least one of the indoleamines.

A liquid crystal alignment agent characterized by comprising the polymer of the above 2.

A liquid crystal alignment film obtained by using the liquid crystal alignment agent of the above three.

A liquid crystal display device comprising the liquid crystal alignment film of the above four.

By the present invention, it is possible to provide a novel diamine which is capable of obtaining a liquid crystal alignment film which is reduced in variation in liquid crystal alignment properties driven by AC. Then, since the liquid crystal alignment film obtained by using the diamine does not easily change due to the alignment property of the liquid crystal driven by the AC, the liquid crystal display element having the liquid crystal alignment film can obtain an effect of preventing image sticking.

[Best Mode for Carrying Out the Invention]

The invention is described in detail below.

The diamine of the present invention is a diamine represented by the above formula (1). In the formula (1), the so-called cinnabarinyl group is a structure represented by the following formula.

Further, in the formula (1), the position of the amine group (-NH ₂ ) which the benzene ring has is not particularly limited, and from the viewpoint of liquid crystal alignment performance or ease of synthesis, it is preferably, for example, relative to -X ¹ - X ² -X ³ -X ⁴ -X ⁵ - are present in the para or meta position, respectively.

The diamine represented by the formula (1) is, for example, the following diamine.

Wherein X is independently a single bond or a linkage selected from the group consisting of ether (-O-), ester (-COO- or -OCO-), and decylamine (-CONH- or -NHCO-), Y independent The ground is a single bond or an alkylene group having a carbon number of 1 to 5, and Z is independently an alkylene group having a carbon number of 1 to 10 or a phenyl group. The bonding position of the amine group on the benzene ring or the benzene relative to the center The position of the bond group of the ring is not particularly limited).

Specific examples of the diamine represented by the formula (1) include the following diamines.

By using the diamine of the present invention represented by the above formula (1) as a raw material, a polyimine imine precursor such as polyglycolic acid or polyglycolate, polyimine or polyamine is obtained. A liquid crystal alignment film formed using a liquid crystal alignment agent containing the above-mentioned polyimine precursor, polyimine or polyamine, in the aspect of changing the alignment property of the liquid crystal driven by AC (for example, liquid crystal) The change is the lower one. Therefore, in the liquid crystal display element having the liquid crystal alignment film, since the liquid crystal alignment property of the liquid crystal alignment film driven by AC is stable, it is difficult to cause image sticking due to AC driving, that is, the residual image characteristic due to AC driving is extremely high. Good effect. In addition, the liquid crystal alignment film formed by using the diamine represented by the above formula (1) is excellent in liquid crystal alignment performance itself, and can be a liquid crystal alignment film having substantially no alignment defects.

As described above, the diamine represented by the above formula (1) can be used as a liquid crystal alignment film which is reduced in the liquid crystal alignment performance by AC driving, and becomes a liquid crystal which is less likely to cause image sticking due to AC driving. The reason for the display element is not clear, but the reason is presumed as follows: the diamine represented by the formula (1) is used, and the main chain of the polyimine precursor, the polyimine or the polyamine can be introduced. The specific photoreactive group derived from the diamine represented by the formula (1) which imparts an alignment property to the liquid crystal (i.e., -HN-C ₆ H ₄ -X ¹ -X ² -X ³ -X ⁴ -X ⁵ - C ₆ H ₄ -NH-), even if the liquid crystal moves due to AC driving, since the specific photoreactive group derived from the diamine represented by the formula (1) is not easily moved, the alignment orientation is not easily shifted. The reason.

On the other hand, for example, in the present invention, the main chain of the polyimine precursor, the polyimine or the polyamine is introduced from the formula (1). When the structure of the diamine represented is introduced into the side chain of the polyimine precursor, the polyimine or the polyamine, not the main chain, since the side chain is suspended from the main chain, when AC driving is performed, The side chain is moved by the liquid crystal which is moved by the AC drive, and the liquid crystal alignment property of the side chain is shifted by the structure of the diamine represented by the formula (1). The alignment direction is greatly offset, and the image is easily generated due to the AC drive.

The method for synthesizing the diamine represented by the above formula (1) is not particularly limited, and can be produced, for example, according to a synthesis example described later. For example, in the case of the diamine represented by the formula (a), it can be synthesized by the method shown below.

The diamine represented by the above formula (a) can be obtained by synthesizing a corresponding dinitro compound represented by the following formula (a'), and further reducing the nitro group to convert it into an amine group. The method for reducing the dinitro compound is not particularly limited, and generally, palladium-carbon, platinum oxide, nickel nickel, iron, tin chloride, platinum black, barium-aluminum, platinum sulfide carbon or the like can be used as a catalyst. It is effective to use a chemical reduction method using iron or tin chloride from the viewpoint of selectively reducing only the nitro group in a residual state without reducing the olefin. A method in which a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol is used as a reducing agent, and a reaction such as hydrogen, helium, hydrogen chloride or ammonium chloride is used as a reducing agent.

(wherein X and Y are synonymous with X and Y of the formula (a), respectively).

The method for synthesizing the dinitro compound represented by the formula (a') is not particularly limited, and it can be synthesized by any method. As this specific example, it can be synthesized by, for example, the method shown in the following reaction. .

In this reaction, in order to react the nitrobenzene compound A with the compound B having a carboxylic acid, in an organic solvent, for example, by direct condensation using DMAP/DCC or DMAP/EDC, or by using ruthenium ruthenium Tionyl chloride or oxalyl chloride, Phosphoryl chloride, sulfuryl chloride, phosphorus trichloride or the like is used as an acid chloride to cause a reaction, and synthesis can be carried out. Further, the so-called DMAP is 4-N,N-dimethylaminopyridine; the so-called DCC is dicyclohexylcarbodiimide; the so-called EDC is 1-(3-dimethylaminopropyl)- 3-ethylcarbodiimide hydrochloride.

In the above nitrobenzene compound A, X and Y are respectively synonymous with X and Y of the formula (a), and examples thereof include 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, and 4-nitrobenzyl alcohol. , 3-nitrobenzyl alcohol, 2-nitrobenzyl alcohol, 4-nitrophenylethanol, 3-nitrophenylethanol, 2-nitrophenylethanol, etc.; can be inserted between the benzene ring and the hydroxyl group as required Linkage Y. Further, another substituent may be bonded to the benzene ring, and the substitution position of the nitro group on the benzene ring may be appropriately selected depending on the diamine of the intended purpose. The compound shown here is only an example, and is not particularly limited thereto.

As the organic solvent, an aromatic solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as hexane or heptane, or dichloromethane, 1,2- can be used alone as a solvent which does not affect the reaction. A halogen solvent such as dichloroethane, an ether solvent such as tetrahydrofuran or 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-A An aprotic polar solvent such as pyrrolidone or dimethyl hydrazine may be used in combination. Moreover, the usage amount of these is arbitrary.

Other diamines can also be synthesized by using the same method as the diamine represented by the above formula (a).

The polyimine precursor of polyglycosic acid, polyglycolate or the like of the present invention is obtained by including the diamine represented by the above formula (1) The amine component is obtained by reacting with a tetracarboxylic acid component. Further, the polyglycolate can also be obtained by a method of converting a carboxyl group of polylysine to an ester. Then, the polyimine of the present invention can be obtained by subjecting the polyimine precursor such as polylysine or polylysine to ruthenium imidization. Further, the polyamine of the present invention can be obtained by a reaction obtained by reacting a diamine component containing a diamine represented by the above formula (1) with a halide of a dicarboxylic acid in the presence of a base. The reaction may be carried out by reacting a diamine component containing the diamine represented by the above formula (1) with a dicarboxylic acid in the presence of a suitable condensing agent or a base. Polyacrylamide precursors such as polyaminic acid and polyamidomate, polyimine and polyamine are suitable as polymers for obtaining a liquid crystal alignment film. In addition, the diamine represented by the formula (1) contained in the diamine component may be one type or two or more types, and the diamine component may be other than the diamine represented by the formula (1). It may also contain one or more other diamines.

The diamine represented by the above formula (1) may exhibit the effect of the present invention at 10 mol% or more based on the total amount of the diamine component, but is preferably 30 to 100 mol%, more preferably 50~ 100% by mole. However, when it is not specifically described in this specification, the ratio is based on the molar number.

Further, the diamine component is a diamine other than the diamine represented by the above formula (1), and examples thereof include p-phenylenediamine and 2,3,5,6-tetramethyl-p-benzene. Diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6- Diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl Alcohol, 4,6-diaminoresorcinol (4,6- Diaminoresorcinol), 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-di Aminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro -4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamine linkage Benzene, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodi Phenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl Base-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4, 4'-diaminodiphenylamine, 3,3'-diamine Diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4 , 4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine , N-methyl (2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminodiphenyl Ketone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2 , 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4 - Bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4 - bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-double ( 4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4- Phenyl bis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylene double (methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylene bis(methylene) )]Diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1 , 4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[ (3-aminophenyl)methanone], 1,4-phenylphenylbis(4-aminobenzoate), 1,4-phenylphenylbis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl) terephthalate Ester, bis(3-aminophenyl)terephthalate, isophthalic acid Bis(4-aminophenyl) acid, bis(3-aminophenyl) isophthalate, N,N'-(1,4-phenylene) bis(4-aminobenzamide) Amine, N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzene Methionine), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalic acid Amine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-double (3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl) Hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis ( 3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3- Bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5- Bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6 - bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8 - bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1, 9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11 -(4-Aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1, 12-(3-Aminophenoxy)dodecane, 4-(aminomethyl)aniline, 3-(aminomethyl)aniline, 3-((aminomethyl)methyl)aniline, 4 -(2-Aminoethyl)aniline or 3-(2-Amino B An aromatic diamine such as aniline; an alicyclic diamine such as bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane; 1,3-diamine Propane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino An aliphatic diamine such as octane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane .

The above-mentioned other diamines may be used in combination of one or two or more kinds in combination with the properties of the liquid crystal alignment, the voltage holding ratio, and the storage charge when the liquid crystal alignment film is formed.

The so-called tetracarboxylic acid component is selected from the group consisting of tetracarboxylic acid and tetracarboxylic acid. At least one of the acid derivatives. Examples of the tetracarboxylic acid derivative include a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, and a tetracarboxylic acid diester. For example, polylysine can be obtained by reacting a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride or the like with a diamine component. Further, by reacting a tetracarboxylic acid diester dichloride with a diamine component, or by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or a base, a polyfluorene can be obtained. Amine ester. Further, the tetracarboxylic acid component may be one type or two or more types.

The tetracarboxylic acid component is, for example, a tetracarboxylic dianhydride represented by the following formula (3).

(In the formula (3), Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).

In the formula (3), a specific example of Z ₁ is, for example, a tetravalent organic group represented by the following formula (3a) to formula (3j).

(In the formula (3a), Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively; in the formula (3g), Z ₆ and Z ₇ are a hydrogen atom or a methyl group. , can be the same or different).

In the formula (3), the structure of Z ₁ is particularly excellent in terms of polymerization reactivity or ease of synthesis, and is a formula (3a), a formula (3c), a formula (3d), a formula (3e), a formula (3f) or Formula (3g). Further, it is preferably a formula (3a), a formula (3e), a formula (3f) or a formula (3g).

In addition, the ratio of the tetracarboxylic dianhydride represented by the formula (3) to the total amount of the tetracarboxylic acid component is not particularly limited, and for example, the tetracarboxylic acid component may be only four as shown by the above formula (3). Carboxylic dianhydride. As a matter of course, the tetracarboxylic acid component may contain a tetracarboxylic acid or a tetracarboxylic acid derivative other than the tetracarboxylic dianhydride represented by the above formula (3) within a range that does not impair the effects of the present invention. In this case, the tetracarboxylic dianhydride represented by the above formula (3) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% of the total amount of the tetracarboxylic acid component. More than 8% of the ear.

Examples of the tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the above formula (3) include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5, 6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3' , 4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4 '-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl) Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane , bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3 ',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid .

The tetracarboxylic acid diester is also not particularly limited. This specific example is exemplified below.

Specific examples of the aliphatic tetracarboxylic acid diester include, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-ring. Dialkyl butane tetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Alkyl ester, dialkyl 1,2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexyl succinate, 3,4-dicarboxy-1, Dialkyl 2,3,4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butanetetracarboxylate, bicyclo[3,3,0]octane-2, Dialkyl 4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentylacetate Ester, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]decane- 3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2, 3,4-tetrahydronaphthalene-1,2-dicarbodialkyl ester and the like.

As the aromatic tetracarboxylic acid dialkyl ester, for example, dialkyl pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, 2, 2', 3, 3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone tetracarboxylic acid Dialkyl acid ester, dialkyl 2,3,3',4-benzophenone tetracarboxylate, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4- Dicarboxyphenyl)stilbene dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, and the like.

The dicarboxylic acid or the like which is used to obtain the polyamine of the present invention and reacts with the diamine component is not particularly limited. Specific examples of the aliphatic dicarboxylic acid as the dicarboxylic acid or a derivative thereof for reacting the polyamine with the diamine component include malonic acid, oxalic acid, dimethylmalonic acid, and succinic acid. Fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipate, trimethyl adipate, pimelic acid, 2,2-dimethylglutaric acid, 3,3-di Dicarboxylic acids such as ethyl succinic acid, azelaic acid, sebacic acid and suberic acid.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, and 1,2-cyclobutylene. Alkanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane Dicarboxylic acid, 1-cyclobutylene-1,2-dicarboxylic acid, 1-cyclobutylene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-ring Pentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-northene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4 -dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3- Adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid, etc. .

Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butyl isophthalic acid, and 5-amino group. Phthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 1,4-quinone dicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4, 4'-biphenyldicarboxylic acid, 1,5-extended biphenyl dicarboxylic acid, 4,4"-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4, 4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether Carboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-diphenylacetylene dicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4 , 4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid , p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenebis-p-phenylene)dipropionic acid, 4,4 -[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylphenyl)]butyric acid, A dicarboxylic acid such as (isopropene di-p-phenylenedioxy)dibutyric acid or bis(p-carboxyphenyl)dimethyloxane.

Examples of the dicarboxylic acid containing a hetero ring include 1,5-(9-oxoindole)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, and 2-phenyl- 4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridine Dicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid and the like.

The above various dicarboxylic acids may be structural builders of acid dihalides or anhydrides. It is preferable that these dicarboxylic acids are in particular a dicarboxylic acid which can impart a linear structure to a polycarboxylic acid, and it is preferable to maintain the alignment of the liquid crystal molecules. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyl is preferably used. Methane dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2,2 - bis(phenyl)propane dicarboxylic acid, 4,4"-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid or the like of such acid dihalides These compounds may be contained in the presence of the isomers, or may be a mixture containing the above. Further, two or more kinds of compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above-exemplified examples. Compound.

The tetracarboxylic dianhydride represented by the above formula (3), or other tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid, or the like, liquid crystal alignment, voltage retention, and storage in the case of forming a liquid crystal alignment film The desired properties such as electric charges may be used in combination of one type or two or more types.

The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in an organic solvent. As the organic solvent used at this time, as long as it is already The polyimine precursor such as the produced polyamic acid is soluble, and is not particularly limited. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and dimethylene. Bismuth, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylene hydrazine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl fluorenyl Ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cystatin, cesetux, acesulfame acetate, acetaminophen acetate, butyl carbitol, Ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol -tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl -3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, Propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propyl carbonate ( Propylene carbonate), methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Methyl ester, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate , 3-methoxypropionic acid butyl ester, digans Methyl ether or 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. Further, even if the polyimide precursor is a solvent which is insoluble, it may be used in the above solvent as long as it is within a range in which the produced polyimide precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried by dehydration.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly or a method of adding or dispersing or dissolving in an organic solvent; conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent; and interacting a tetracarboxylic acid component with a diamine component Any of these methods can be used for the method of addition or the like. Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a state of being mixed beforehand, or the reaction may be carried out in an individual order, and the low molecular weight body after the individual reaction may be further obtained. The reaction was mixed again. The polymerization temperature at this time may be any temperature of from -20 ° C to 150 ° C, but preferably from -5 ° C to 100 ° C. Further, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a high molecular weight polyimine precursor (or even a polyimide); if the concentration is too high, the viscosity of the reaction solution is high. It will be too high and it will become difficult to evenly stir. Therefore, the concentration of the total amount of the diamine component and the tetracarboxylic acid component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total amount of the reaction solution. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added.

Polymerization of polyamidiamine precursors such as polylysine The ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

Further, the polyglycolate may be reacted with a dicarboxylic acid diester dichloride component and a diamine component as described above, or by a tetracarboxylic acid diester and a diamine component in a suitable condensing agent or alkali It is obtained by the reaction in the presence of it. Alternatively, the polyamic acid may be synthesized in advance by the above method, and the carboxyl group of the polylysine may be esterified by a polymer reaction.

Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine component are carried out in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. The polyamine derivative can be synthesized in an hour, preferably from 1 hour to 4 hours.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, and for the purpose of the reaction being stable, pyridine is preferred. The amount of the base to be added is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of the polymer.

Further, when the tetracarboxylic acid diester and the diamine component are subjected to polycondensation in the presence of a condensing agent, triphenylphosphite, dicyclohexylcarbodiimide or 1-ethyl-3- can be used as the base. (3-dimethylaminopropyl) carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-three Methylmorpholine oxime, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazole-1 -yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid diphenyl Ester, 4-(4,6-dimethoxy-1,3,5-three -2-yl) 4-methoxymorpholine chloride n-hydrate and the like.

Further, in the method of using the above condensing agent, the reaction can be efficiently carried out by adding a Lewis acid as an additive. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The amount of the Lewis acid to be added is preferably 0.1 to 1.0 times the molar amount relative to the diamine or tetracarboxylic acid diester to be reacted.

The solvent used in the above reaction can be carried out by using the same solvent as that used in the above-mentioned synthesis of polyamic acid, but in terms of the solubility of the monomer and the polymer, N- is preferable. Methyl-2-pyrrolidone and γ-butyrolactone may be used alone or in combination of two or more. The concentration at the time of the synthesis is a tetracarboxylic acid derivative such as a tetracarboxylic acid diester dichloride or a tetracarboxylic acid diester, and the like, insofar as the polymer is less likely to be precipitated and the polymer is easily obtained. The total concentration in the reaction solution of the amine component is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferably used in the synthesis of the polyphthalate to be dehydrated as much as possible, preferably in a nitrogen atmosphere to prevent the incorporation of outside air. .

The polyimine precursor polymerized in such a manner has a polymer having a repeating unit represented by the following formula [a], for example.

(In the formula [a], R ₁₁ is a tetravalent organic group derived from a tetracarboxylic acid component of a raw material, R ₁₂ is a divalent organic group derived from a diamine component of a raw material, and A ₁₁ and A ₁₂ are a hydrogen atom or carbon. The alkyl groups of 1 to 4 may be the same or different, and j is a positive integer.

In the above formula [a], R ₁₁ and R ₁₂ may each be a polymer having the same and one type of repeating unit, and R ₁₁ or R ₁₂ may also be a polymer having repeating units of different and plural configurations. .

In the above formula [a], R ₁₁ is a group derived from a tetracarboxylic acid component represented by the following formula [c] or the like from a raw material. Further, R ₁₂ is a group derived from a diamine component represented by the following formula [b] or the like from the raw material. For example, when R ₁₂ is a group derived from the diamine represented by the above formula (1), it is - C ₆ H ₄ -X ¹ -X ² -X ³ -X ⁴ -X ⁵ -C ₆ H ₄ -. In the case where the diamine represented by the above formula (1) is used as a raw material, the main chain is introduced with -HN-C ₆ H ₄ -X ¹ -X as shown in the above formula [a]. ² -X ³ -X ⁴ -X ⁵ -C ₆ H ₄ -NH-polyimine precursor.

(In the formula [b] and the formula [c], R ₁₁ and R ₁₂ are the same as those defined in the formula [a]).

Then, the polyimine is obtained by dehydrating and ring-closing such a polyimide precursor.

As a method for imidating a polyimine precursor ruthenium, for example, a ruthenium imidization in which a solution of a polyimide precursor is directly heated, or a catalyst added to a solution of a polyimide precursor The catalyst is imidized.

When the polyimine precursor is thermally imidized in a solution, the temperature is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water side formed by the imidization reaction is preferably used. Exclude from the outside of the line to carry out the reaction.

The ruthenium imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, and is -20 to 250 ° C, preferably 0 to 180. It can be carried out by stirring at °C. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group; the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine can be exemplified, among which pyridine is especially used. The reaction is moderately alkaline, so it is preferred. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, in particular, when acetic anhydride is used, purification after completion of the reaction is easy, and therefore it is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

Further, when the polyimine precursor or the polyimine of poly-proline or polyphthalamide is used to recover the produced polyimine precursor or polyimine from the reaction solution, The reaction solution is poured into a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, acetone, hexane, butyl sulphate, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or water. The precipitated polyimine precursor or polyimine is filtered and recovered, and then dried under normal pressure or under reduced pressure at normal temperature or under reduced pressure. Further, the polyimine precursor or the polyimine which has been precipitated and recovered is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated for 2 to 10 times to reduce the polyimine precursor or the polyfluorene. Impurities in the amine. The solvent in this case is, for example, an alcohol, a ketone or a hydrocarbon. When three or more solvents selected from the group consisting of these are used, the efficiency of purification can be further improved.

The dehydration ring closure ratio of the amidino group of the polyimine (the ruthenium imidation ratio) is not necessarily 100%, and may be arbitrarily selected in the range of 0% to 100% depending on the purpose or purpose, but preferably 50%. ~100%.

Polyamine can also be synthesized in the same manner as polyglycolate.

Polyimine precursor, polyimide or polyfluorene of the present invention The molecular weight of the amine, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the obtained polymer film (liquid crystal alignment film), the workability when the polymer film is formed, and the uniformity of the polymer film are considered. It is preferably set to 5,000 to 1,000,000, more preferably 10,000 to 150,000.

The liquid crystal alignment agent of the present invention is a polyimine precursor containing polyacrylamide, polyphthalamide or the like, polyimine or polyamine. The liquid crystal alignment agent is a solution for forming a liquid crystal alignment film, and is a solution for dispersing or dissolving a polymer component for forming a liquid crystal alignment film in an organic solvent. Further, a so-called liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction. In the present invention, the polymer component contains a polyimine precursor selected from the above-described polylysine, polylysine or the like of the present invention, polyimine and polyamine. At least one.

The polymer component contained in the liquid crystal alignment agent of the present invention may be the polyimine precursor such as polylysine or polylysine of the present invention, polyimine or polyamine, and Further, other polymers may be mixed in the polyimine precursor, polyethylenimine or polyamine of the above polylysine, polyphthalate or the like of the present invention. When the polymer component contains another polymer, the content of the other polymer in the total amount of the polymer component is 0.5% by mass to 50% by mass, preferably 1% by mass to 30% by mass.

As such a other polymer, for example, a diamine component which reacts with a tetracarboxylic dianhydride component or a dicarboxylic acid, etc., is used, for example, only the diamine represented by the above formula (1) of the present invention is used. Diamine Polyimine precursor, polyimine or polyamine. More specifically, for example, an acrylic polymer, a methacrylic polymer or polystyrene is also mentioned.

In the liquid crystal alignment agent of the present invention, at least one selected from the group consisting of polyacrylamide precursors such as polylysine and polylysine of the present invention, polyimine and polyamine, and The content ratio of the other polymer to be mixed is preferably from 1% by mass to 20% by mass based on the total amount of the polymer component, more preferably from 3% by mass to 15% by mass, particularly preferably from 3% by mass to 10% by mass.

The solvent to be contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a polymer component which can dissolve the polyimine precursor of the present invention, polyimine or polyamine. As such a specific example, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2 - pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylene hydrazine, γ-butyrolactone, 3- Methoxy-N,N-dimethylpropane decylamine, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, 1 , 3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, carbonic acid Ester, propyl carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination.

The liquid crystal alignment agent of the present invention may contain an organic solvent for improving the uniformity of the film thickness or the surface smoothness of the polymer film when the liquid crystal alignment agent is applied, without impairing the effects of the present invention. (also known as weak solvent) or compound. Further, it may also contain a liquid crystal alignment film and A compound in which the adhesion of the substrate is improved.

A weak solvent which improves the uniformity of the film thickness or the surface smoothness, and examples of the solvent include, for example, isopropyl alcohol, methoxymethylpentanol, acesulfur, cesasu, dicetaxan, acetic acid.赛赛路苏,Acetylacetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol single Acetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, two Propylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl Alcohol, diisopropyl ether, ethyl isobutyl ether, isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether , n-self , n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl Ethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactate n- An organic solvent having a low surface tension, such as a propyl ester, n-butyl lactate or isoamyl lactate.

These weak solvents can be used in one type or in combination of plural kinds. When a solvent as described above is used, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, F-Top EF301, EF303, EF352 (manufactured by Tokem Products), Megaface F171, F173, R-30 (made by Dainippon Ink), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Aashiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass). The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

Examples of the compound which enhances the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group, and examples thereof include 3-aminopropyltrimethoxydecane and 3-aminopropyl. Triethoxy decane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecyl propyl triethylene glycol triamine, N-trimethoxydecyl propyl tris-ethyltriamine, 10-trimethoxydecyl-1, 4, 7 - triazane, 10-triethoxydecyl-1,4,7-triazane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethyl Oxidylalkyl-3,6-diazadecyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylidene)-3-aminopropyltrimethyl Oxydecane, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, three Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol Diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1 , 3- Bis(N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane or the like.

When a compound which improves the adhesion to the substrate is used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. Share. When the amount used is less than 0.1 mass, the effect of improving the adhesion cannot be expected; when the amount used is more than 30 parts by mass, the alignment of the liquid crystal is deteriorated.

In the liquid crystal alignment agent of the present invention, in addition to the above, the dielectric of the liquid crystal alignment film is changed within a range not impairing the effects of the present invention. For the purpose of electrical properties such as rate or conductivity, a dielectric or a conductive substance may be added; and a crosslinkable compound for improving the hardness or density of the film at the time of forming a liquid crystal alignment film may be added.

The liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film by being subjected to alignment treatment by rubbing treatment or light irradiation (radiation irradiation), which is applied to a substrate and fired. The liquid crystal alignment film of the present invention is formed by using a polyimine precursor, a polyimine or a polyamine which uses the diamine represented by the above formula (1) as a raw material, so that the alignment property of the liquid crystal is not easy. It changes due to AC drive.

The substrate is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed. Further, in the reflective liquid crystal display device, when it is only a single-sided substrate, an opaque substrate such as a germanium wafer may be used. In this case, a material such as aluminum that reflects light may be used as the electrode. Further, in a high-performance element such as a TFT-type element, it is used between an electrode and a substrate to form an element for liquid crystal driving such as a transistor.

The coating method of the liquid crystal alignment agent is not particularly limited, but industrially, it is generally a method of performing screen printing, dry lithography, quick-drying printing, or inkjet method. As another coating method, there are a dipping method, a roll coating method, a slit coating method, a spin coating method, a spray method, and the like, and these coating methods can be used depending on the purpose.

After the liquid crystal alignment agent is coated on the substrate, by heating In a heating means such as a plate, a heat cycle type oven or an IR (infrared) type oven, the solvent is evaporated at 50 to 300 ° C, preferably 80 to 250 ° C, to form a liquid crystal alignment film (polymer film). The thickness of the liquid crystal alignment film after firing is unfavorable in terms of power consumption of the liquid crystal display element when it is too thick; when it is too thin, since the reliability of the liquid crystal display element is lowered, it is preferably 5 to 300 nm. More preferably, it is 10 to 100 nm. When the liquid crystal is aligned in a horizontal alignment or a tilt direction, the liquid crystal alignment film after firing is treated by rubbing or polarized ultraviolet irradiation or the like to align the liquid crystal. For example, by irradiation with light such as polarized ultraviolet light, the photoreactive group derived from the diamine represented by the formula (1) undergoes a dimerization reaction, whereby the liquid crystal is aligned by the anisotropy.

In the liquid crystal display device of the present invention, after the substrate having the liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above-described method, a liquid crystal cell is produced by a known method, and a liquid crystal display element is obtained. In the case of the liquid crystal display element having the liquid crystal cell, the liquid crystal cell has two substrates arranged in a facing manner, a liquid crystal layer disposed between the substrates, and a liquid crystal layer disposed between the substrate and the liquid crystal layer. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention. As such a liquid crystal display element of the present invention, for example, an IPS (In-Plane Switching) method, a TN (Twisted Nematic) method, an OCB (Optically Compensated Bend), or a vertical alignment ( Various types such as VA: Vertical Alignment). In addition, the liquid crystal alignment film may be provided in at least one of the two substrates.

As a base used in the liquid crystal display element of the present invention The plate is not particularly limited as long as it is a substrate having high transparency, but usually a substrate on which a transparent electrode for driving liquid crystal is formed is formed on the substrate. As a specific example, the same substrate as the substrate described in the above liquid crystal alignment film can be exemplified.

Further, in the liquid crystal alignment film, the liquid crystal alignment agent of the present invention is applied onto the substrate, and then fired, and if necessary, formed by rubbing treatment or irradiation with radiation such as polarized ultraviolet rays, as described above.

In the liquid crystal display device of the present invention, the liquid crystal material constituting the liquid crystal layer is not particularly limited, and a positive type liquid crystal having positive dielectric anisotropy or a negative type liquid crystal having negative dielectric anisotropy can be used. As a specific example, in the liquid crystal material used in the conventional horizontal alignment method, for example, MLC-2041 manufactured by Merck Co., Ltd. or the like can be used.

For example, in the case of producing a liquid crystal cell, a method in which a pair of substrates on which a liquid crystal alignment film has been formed is prepared, and a spacer such as beads is spread on a liquid crystal alignment film of one of the substrates, a method in which the liquid crystal alignment film surface is bonded to the other substrate, and the liquid crystal is injected under reduced pressure and sealed; or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer is dispersed, and the substrate is pasted and sealed. The method. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm. Then, in the case of the liquid crystal display element of the horizontal alignment type, after the liquid crystal is sealed as described above, a polarizing plate is disposed on the outer side of the substrate.

As described above, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention has a liquid crystal alignment film, which suppresses a change in the alignment property of the liquid crystal driven by the AC, so that the image retention property can be extremely It is excellent in liquid crystal display elements which are not easily burnt and which are less likely to cause poor display or contrast reduction.

[Examples]

The following is explained in more detail based on the examples, but the invention is not limited to the examples.

The abbreviation used in this embodiment is as follows.

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

DA-1: a diamine represented by the following formula

Diamines represented by the following formula [1]~[7]

Diamines represented by the following formula [8]~[12]

< ¹ H-NMR Measurement>

The measurement conditions of ¹ H-NMR in the synthesis examples are as follows.

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (Varian) 400MHz

Solvent: dimethyl hydrazine (DMSO-d ₆ ), chloroform (CDCl ₃ )

Reference material: tetramethyl decane (TMS)

<Polymer molecular weight determination>

Further, the molecular weight measurement conditions of the polymer (polyproline or the like) are as follows.

Device: room temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Senshu Scientific co., Ltd., column: Shodex column (KD-803, KD-805)

Column temperature: 50 ° C

Dissolving agent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H ₂ O) 30 mmol/L, phosphoric acid. anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0ml/min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Synthesis of diamine> (Synthesis Example 1) Synthesis of Diamine [1] ((E, E)-Bis-(4'-aminophenyl) 1,4-benzenediacrylate)

To a 2 L four-necked flask, terephthalaldehyde [A] (40.00 g, 298 mmol), pyridine (46 g), and piperidine (7.0 g) were added, and the reaction solution was heated to 100 ° C while stirring. At this time, a pyridine solution (500 g) of malonic acid [B] (140.0 g, 1.34 mol) was dropped. After confirming the completion of the reaction by HPLC (High Performance Liquid Chromatography), the reaction solution was cooled to 40 ° C, and the reaction solution was poured into distilled water (1 L). Next, concentrated hydrochloric acid was added until the reaction solution became acidic, and then the solid was filtered, washed with water, washed with methanol, and dried under reduced pressure to give compound [C] (yield: 60.3 g, yield: 93%). The results of ¹ H-NMR measurement of the obtained compound [C] are as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 12.4 (2H, brs), 7.74 (4H, s), 7.60 (2H, d), 6.61 (2H, d).

Next, a compound [C] (30.00 g, 138 mmol), 4-nitrophenol [D] (42.08 g, 303 mmol), and 1-ethyl-3-(3-dimethylamino group) were added to a 1 L four-necked flask. Propyl) carbodiimide hydrochloride (hereinafter referred to as EDC) (68.53 g, 358 mmol), 4-N,N-dimethylaminopyridine (hereinafter referred to as DMAP) (3.56 g, 27.5 mmol), tetrahydrofuran ( Hereinafter, it is abbreviated as THF) (600 g), and it stirred at 23 degreeC. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a mixed solution of ethyl acetate (500 mL) / distilled water (1 L), and the solid was filtered, washed with a 1:1 mixed solution of ethyl acetate/methanol, and The compound [E] (yield: 60.6 g, yield: 96%) was obtained by drying under reduced pressure. The results of ¹ H-NMR measurement of the obtained compound [E] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 8.36-8.31 (4H, m), 7.92 (2H, d), 7.68 (4H, s), 7.40-7.37 (4H, m), 6.70 ( 2H, d).

Next, a compound [E] (63.30 g, 138 mmol), tin chloride (182.5 g, 962 mmol), THF (630 g), and distilled water (440 g) were added to a 2 L four-neck flask, and the mixture was heated and stirred at 70 °C. After confirming the completion of the reaction by HPLC, after adding N,N-dimethylacetamide (1 L), the reaction solution was diluted with ethyl acetate (2.5 L), and sodium hydrogencarbonate was added until the by-product tin hydroxide was not Precipitated. Thereafter, the supernatant was filtered, and the filtrate was separated and the aqueous layer was removed. Thereafter, the organic layer was washed successively with 1 L of a saturated aqueous sodium hydrogen carbonate solution (2 s) and brine (2 s), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off using an evaporator, and after obtaining a crude product, methanol (200 mL) was added, and the mixture was stirred at room temperature (23 ° C) for 30 minutes, and then filtered again, washed with methanol, and decompressed by methanol. The mixture was dried to give a diamine [1] (yield: 24.0 g, yield: 44%). The results of ¹ H-NMR measurement of the obtained diamine [1] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.83 (4H, s), 7.79 (2H, d), 6.89 (2H, d), 6.81-6.78 (4H, m), 6.56-6.53 ( 4H, m), 5.04 (4H, brs).

(Synthesis Example 2) Synthesis of diamine [2] ((E, E)-Bis-(4'-aminophenylethyl) 1,4-benzenediacrylate)

Compound [C] (30.21 g, 138 mmol), 2-(4-nitrophenyl)ethanol [F] (50.91 g, 305 mmol), EDC (68.98 g, 360 mmol), DMAP (3.38) were added to a 1 L four-neck flask. g, 27.9 mmol) and THF (600 g) were stirred at 23 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a mixed solution of ethyl acetate (1 L) / distilled water (1 L), and then The solid was filtered, washed with a 1:1 mixed solution of ethyl acetate/methanol, and dried under reduced pressure to give compound [G] (yield: 70.9 g, yield: 99%).

Next, a compound [G] (71.48 g, 138 mmol), tin chloride (183.4 g, 969 mmol), THF (715 g), and distilled water (500 g) were added to a 2 L four-neck flask, and the mixture was heated and stirred at 70 °C. After confirming the completion of the reaction by HPLC, after adding N,N-dimethylacetamide (1 L), the reaction solution was diluted with ethyl acetate (2.5 L), and sodium hydrogencarbonate was added until the by-product tin hydroxide was not Precipitated. Thereafter, the supernatant was filtered, and the filtrate was separated and the aqueous layer was removed. Thereafter, the organic layer was washed successively with 1 L of a saturated aqueous sodium hydrogen carbonate solution (2 s) and brine (2 s), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off using an evaporator, and after obtaining a crude product, methanol (200 mL) was added thereto, and the mixture was stirred at room temperature for 30 minutes, and then filtered again, washed with methanol, and dried under reduced pressure. Amine [2] (capacity: 30.6 g, yield: 48%). The resulting diamine [2] The measurement results of ¹ H-NMR as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.66 (2H, d), 7.73 (4H, s), 7.60 (2H, d), 6.90-6.88 (4H, m), 6.66 (2H, d), 6.45-6.46 (4H, m), 4.88 (4H, brs), 4.21 (4H, t), 2.75 (4H, t).

(Synthesis Example 3) Synthesis of Diamine [3] ((E, E)-Bis-(4'-aminophenyl)1,3-benzenediacrylate)

To a 2 L four-necked flask, isophthalaldehyde [H] (50.00 g, 373 mol), pyridine (78 g), and piperidine (9.5 g) were added, and the reaction solution was heated to 100 ° C while stirring. At this time, a pyridine solution (600 g) of malonic acid [B] (169.5 g, 1.68 mol) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was cooled to 40 ° C, and the reaction solution was poured into distilled water (1 L). Next, concentrated hydrochloric acid was added until the reaction solution became acidic, and then the solid was filtered and washed with water to obtain a crude product of the compound [I]. This crude product was stirred at room temperature for 30 minutes with a 1:1 mixed solution of ethyl acetate/methanol, and filtered, washed with ethyl acetate, and dried under reduced pressure to give compound [I] (yield: 80.2 g, yield: 99%). The results of ¹ H-NMR measurement of the obtained compound [I] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 12.4 (2H, brs), 8.07 (1H, s), 7.72 (2H, dd), 7.61 (2H, d), 7.46 (1H, t) .

Next, a compound [I] (30.00 g, 138 mmol), 4-nitrophenol [D] (40.17 g, 289 mmol), EDC (63.26 g, 330 mmol), DMAP (3.36 g, 27.5 mmol) were added to a 1 L four-neck flask. ), THF (600 g), and stirred at 23 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a mixed solution of ethyl acetate (500 mL) / distilled water (1 L), and the solid was filtered, washed with ethyl acetate, and dried under reduced pressure to give a compound [ J] (capacity: 62.1 g, yield: 98%). The results of ¹ H-NMR measurement of the obtained compound [J] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 8.37 (1H, s), 8.32-8.29 (4H, m), 7.92 (2H, d), 7.88 (2H, dd), 7.56-7.51 ( 5H, m), 7.08 (2H, d).

Next, a compound [J] (62.1 g, 135 mmol), tin chloride (182.5 g, 962 mmol), THF (630 g), and distilled water (630 g) were added to a 2 L four-neck flask, and the mixture was heated and stirred at 70 °C. After confirming the completion of the reaction by HPLC, the reaction solution was diluted with ethyl acetate (2 L), and sodium hydrogen carbonate was added until the tin hydroxide of the by-product was not precipitated. Thereafter, the supernatant was filtered, and the filtrate was separated and the aqueous layer was removed. Thereafter, the organic layer was washed successively with 1 L of a saturated aqueous sodium hydrogen carbonate solution (2 s) and brine (2 s), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off using an evaporator, and after obtaining a crude product, methanol (200 mL) was added thereto, and the mixture was stirred at room temperature for 30 minutes, and then filtered again, washed with methanol, and dried under reduced pressure. Amine [3] (capacity: 34.1 g, yield: 54%). The results of ¹ H-NMR measurement of the obtained diamine [3] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 8.27 (1H, s), 7.82-7.77 (4H, m), 7.49 (1H, t), 6.96 (2H, d), 6.82-6.78 ( 4H, m), 6.56-6.53 (4H, m), 5.04 (4H, brs).

(Synthesis Example 4) Synthesis of diamine [4] ((E, E)-Bis-(4'-aminophenylethyl)1,3-benzenediacrylate)

Compound [I] (54.92 g, 252 mmol), 2-(4-nitrophenyl)ethanol [F] (92.58 g, 554 mmol), EDC (125.4 g, 654 mmol), DMAP (6.15) were added to a 1 L four-neck flask. g, 50.3 mmol), THF (1.1 Kg), stirred at 23 °C. After confirming the completion of the reaction by HPLC, ethyl acetate (1 L) / hexane (500 mL) / distilled water (1 L) was added to the reaction solution, and the aqueous layer was removed by a liquid separation operation. Thereafter, the organic layer was washed three times with brine (1 L), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off using an evaporator to obtain a crude product of compound [K]. Methanol (300 g) was added to the crude product, and the mixture was stirred at room temperature for 30 minutes, and then filtered and dried under reduced pressure to give compound [K] (yield: 82.2 g, yield: 63%). The results of ¹ H-NMR measurement of the obtained compound [K] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 8.17-8.14 (4H, m), 8.11 (1H, s), 7.70 (2H, dd), 7.62 (1H, s), 7.59-7.56 ( 5H, m), 7.42 (1H, t), 6.71 (2H, d), 4.41 (4H, t), 3.10 (4H, t).

Next, a compound [K] (82.21 g, 139 mmol), tin chloride (211.3 g, 1.11 mol), THF (820 g), and distilled water (820 g) were added to a 2 L four-neck flask, and the mixture was heated and stirred at 70 °C. After confirming the completion of the reaction by HPLC, the reaction solution was diluted with ethyl acetate (2.5 L), and sodium hydrogen carbonate was added until the tin hydroxide of the by-product was not precipitated. Thereafter, the supernatant was filtered, and the filtrate was separated and the aqueous layer was removed. Thereafter, the organic layer was washed successively with 1 L of a saturated aqueous sodium hydrogen carbonate solution (2 s) and brine (2 s), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off using an evaporator, and after obtaining a crude product, methanol (200 mL) was added thereto, and the mixture was stirred at room temperature for 30 minutes, and then filtered again, washed with methanol, and dried under reduced pressure. Amine [4] (capacity: 46.1 g, yield: 73%). The results of ¹ H-NMR measurement of the obtained diamine [4] are as follows.

^{1 H-NMR (400MHz, CDCl3} , δ ppm): 7.66 (2H, d), 7.63 (1H, s), 7.54-7.39 (1H, m), 7.07-7.04 (4H, m), 6.68-6.65 (4H , m), 6.45 (2H, d), 5.04 (4H, brs), 4.37 (4H, t), 2.91 (4H, t).

(Synthesis Example 5) Synthesis of diamine [5] ((E)-4-aminophenethyl 3-(4-aminophenyl)acrylate)

Add compound [M] (12.7 g, 65.8 mmol), 2-(4-nitrophenyl)ethanol [F] (10 g, 59.8 mmol), EDC (15 g, 77.7 mmol), DMAP (500 ml) to a 500 mL reaction vessel. 365 mg, 3 mmol) and 200 g of THF were substituted with nitrogen and stirred at room temperature. After completion of the reaction, distilled water (2 L) was poured into the reaction liquid, and the obtained crystal was washed with isopropyl alcohol (100 g) to obtain a compound [N] (yield: 18.4 g, yield: 90%).

The compound [N] (22.4 g, 65.5 mmol) obtained above, tin (II) chloride (80 g, 458.7 mmol), 200 g of THF, and 100 g of distilled water were added to a 500 mL reaction vessel, and the mixture was heated and stirred at 60 °C. After completion of the reaction, sodium hydrogencarbonate was added to the reaction liquid for neutralization, and extraction was carried out with ethyl acetate. After distilling off the solvent, the yellow crystals were dried to give a diamine [5] (yield: 14.0 g, yield: 76%). The results of ¹ H-NMR measurement of the obtained diamine [5] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.46 (1H, d), 7.37 (2H, d), 6.92 (2H, d), 6.56-6.47 (4H, m), 6.20 (1H, d), 5.78 (2H, s), 4.89 (2H, s), 4.18 (2H, t), 2.74 (2H, t).

(Synthesis Example 6) Synthesis of diamine [6] ((2E, 2'E)-pentane-1, 5-diyl bis(3-(4-aminophenyl)acrylate)

Compound [M] (37.5 g, 160.2 mmol), compound [O] (6.4 g, 61.6 mmol), EDC (41.6 g, 172.5 mmol), DMAP (828 mg, 6.8 mmol), and THF 300 g were added to a 500 mL reaction vessel. Stir at room temperature. After completion of the reaction, distilled water (2 L) was poured into the reaction liquid to obtain crystals. The precipitated crystals were dried under reduced pressure to give Compound [P] (30 g).

The compound [P] (15 g, 33.0 mmol) obtained above, tin (II) chloride (43.8 g, 231.0 mmol), 150 g of THF, and 150 g of distilled water were added to a 500 mL reaction vessel, and the mixture was heated and stirred at 60 °C. After completion of the reaction, sodium hydrogencarbonate was added to the reaction liquid for neutralization, and extraction was carried out with ethyl acetate. After distilling off the solvent, the yellow crystals were washed with ethyl acetate and hexane to afford diamine [6] (yield: 11.9 g, yield: 91%). The results of ¹ H-NMR measurement of the obtained diamine [6] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.47 (2H, d), 7.36 (4H, d), 6.55 (4H, d), 6.22 (2H, d), 5.76 (4H, s) , 4.10 (4H, t), 1.99-1.63 (4H, m), 1.46-1.40 (2H, m).

(Synthesis Example 7) Synthesis of diamine [7] ((E)-4-aminophenyl 3-(4-aminophenyl)acrylate)

Compound [M] (34 g, 193.2 mmol), 4-nitrophenol [D] (25.0 g, 179.7 mmol), EDC (40.4 g, 191.7 mmol), DMAP (2.2 g, 18 mmol) were added to a 500 mL reaction vessel. THF 300g, stirred at room temperature. After completion of the reaction, distilled water (3 L) was poured into the reaction liquid, and the precipitated white crystals were each filtered. The obtained crude crystals were washed with isopropyl alcohol (200 g) to give Compound [Q] (52 g, 165.7 mmol).

The above-obtained compound [Q] (30 g, 95.5 mmol), reduced iron (21.0 g, 382 mmol), ammonium chloride chloride (40.8 g, 762.8 mmol), N, N-dimethyl group were added to a 2 L reaction vessel. 200 g of base formaldehyde, 200 g of ethyl acetate, and 400 g of distilled water were heated and stirred at 70 °C. After completion of the reaction, extraction was carried out with ethyl acetate, and after treatment with activated carbon, crude solvent was obtained by distilling off solvent. The obtained crude crystals were purified by washing with methanol and hexane to obtain a diamine [7] (yield: 19.4 g, yield: 80%). The results of ¹ H-NMR measurement of the obtained diamine [7] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.60 (1H, d), 7.43 (2H, d), 6.78 (2H, d), 6.77-6.36 (4H, m), 6.10 (1H, d), 5.85 (2H, s), 5.02 (2H, s).

(Synthesis Example 8) Synthesis of diamine [8] ((E, E)-Bis-(3'-aminophenyl)1,3-benzenediacrylate)

Compound [I] (40.00 g, 183 mmol), 3-nitrophenol [R] (53.56 g, 385 mmol), EDC (84.33 g, 440 mmol), DMAP (4.48 g, 36.7 mmol), and DMAP (4.48 g, 36.7 mmol) were added to a 2 L four-neck flask. THF (800 g) was stirred at 23 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a solution of ethyl acetate (100 mL) / distilled water (1 L), and the solid was filtered and washed with distilled water, ethyl acetate and THF/hexane mixed solvent. The compound [S] (83.5 g, yield 99%) was obtained by drying under reduced pressure. The results of ¹ H-NMR measurement of the obtained compound [S] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 8.37 (1H, s), 8.15-8.13 (4H, m), 7.94-7.87 (4H, m), 7.74-7.72 (4H, m), 7.54 (1H, t), 7.07 (2H, d).

Next, a compound [S] (83.5 g, 181 mmol), iron powder (61.4 g, 1.1 mol), ammonium chloride (29.4 g, 550 mmol), ethyl acetate (760 g), and DMF were added to a 2 L four-neck flask. 500 g), distilled water (260 g), and heated and stirred at 70 °C. After confirming the completion of the reaction by HPLC, the mixture was filtered through a solution of the celite, and ethyl acetate (1 L) was added to the filtrate to carry out liquid separation. The organic layer was washed three times with saturated brine (1 L), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off using an evaporator, and dried under reduced pressure to give a diamine [8] (48.2 g, yield 66%). The results of ¹ H-NMR measurement of the obtained diamine [8] are as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 8.32 (1H, s), 7.83-7.79 (4H, m), 7.50 (1H, t), 7.03-6.97 (4H, m), 6.44 6.41 (2H, m), 6.33-6.32 (2H, m), 6.28-6.25 (2H, m), 5.27 (4H, brs).

(Synthesis Example 9) Synthesis of (E)-3-aminophenyl 3-(4-aminophenyl)acrylate

The same procedure as in Synthesis Example 7 was carried out except that the starting material was changed to 3-nitrophenol [R] to give the diamine [9] (yield: 38 g, yield: 85%). The results of ¹ H-NMR measurement of the obtained diamine [9] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.62 (1H, d), 7.45 (2H, d), 7.01 (1H, t), 6.58 (1H, d), 6.44 (1H, s) , 6.42 (1H, d), 6.31 (1H, d), 6.25 (1H, d), 5.86 (2H, s), 5.25 (2H, s)

(Synthesis Example 10) Synthesis of diamine [10] ((E)-3-aminophenyl 3-(3-aminophenyl)acrylate)

The dinitro compound [T] was obtained in the same manner as in Synthesis Example 7, except that the starting material was changed to the compound [S] and 3-nitrophenol [R]. The obtained dinitro compound [T] was used as a starting compound, and the same operation as in Synthesis Example 7 was carried out to obtain a diamine [10] (yield: 22 g). The results of ¹ H-NMR measurement of the obtained diamine [10] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.60 (1H, d), 7.10 (1H, t), 6.90 (1H, d), 6.88 (1H, s), 6.83 (2H, dt) , 6.68 (1H, d), 6.63 (1H, d), 6.59 (2H, dt), 5.23 (2H, s), 5.06 (2H, s)

(Synthesis Example 11) Synthesis of diamine [11] ((E)-4-aminophenyl 3-(3-aminophenyl)acrylate)

The dinitro compound [U] was obtained in the same manner as in Synthesis Example 7, except that the starting material was changed to the compound [S] and 4-nitrophenol [D]. The obtained compound [T] was used as a starting compound, and the same operation was carried out as in Synthesis Example 7 to give a diamine [11] (yield: 22 g). The results of ¹ H-NMR measurement of the obtained diamine [11] are as follows.

^{1 H-NMR (400MHz, DMSO} -d 6, δ ppm): 7.64 (1H, d), 7.10 (1H, t), 7.04 (1H, t), 6.92-6.88 (2H, m), 6.67 (1H, d), 6.60 (1H, d), 6.46 (1H, d), 6.44-6.34 (1H, m), 6.30-6.27 (1H, m), 5.25 (2H, s), 5.23 (2H, s)

(Synthesis Example 12) Synthesis of diamine [12] ((2E, 2'E)-ethane-1, 2-diyl bis (3-(4-aminophenyl)acrylate))

The dinitro compound [W] was obtained in the same manner as in Synthesis Example 6, except that the starting material was changed to the compound [M] and the ethylene glycol [V]. The obtained dinitro compound [W] was used as a starting compound, and the same operation as in Synthesis Example 6 to give a diamine [12] (yield: 10.2 g). The results of ¹ H-NMR measurement of the obtained diamine [12] are as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm) 8.25-8.23 (4H, d), 8.05-8.02 (4H, d), 7.80 (2H, d), 6.92 (2H, d), 5.76 (4H) , s), 4.40 (4H, s)

(Comparative Synthesis Example 1) Synthesis of Diamine D-1

The diamine DA-1 was synthesized according to Example 1 of JP-A-2001-517719.

<Modulation of liquid crystal alignment agent> (Production of Liquid Crystal Alignment Agent A1)

Add NMP (5.0 g) to diamine [1] (1.20 g, 3.0 mmol) to room After stirring, the mixture was completely dissolved, and then CBDA (0.53 g, 2.8 mmol) and NMP (5.0 g) were added, and the reaction was allowed to stand at room temperature for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A1 was obtained by stirring at room temperature for 5 hours. The polyamine has a number average molecular weight of 6,000 and a weight average molecular weight of 10,500.

(Production of Liquid Crystal Alignment Agent A2)

NMP (5.4 g) was added to the diamine [2] (1.37 g, 3.0 mmol), and stirred at room temperature. After complete dissolution, CBDA (0.55 g, 2.8 mmol) and NMP (5.4 g) were added to the chamber. The reaction was allowed to proceed for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A2 was obtained by stirring at room temperature for 5 hours. The polyamine has a number average molecular weight of 3,800 and a weight average molecular weight of 5,000.

(Production of liquid crystal alignment agent A3)

NMP (5.0 g) was added to the diamine [3] (1.20 g, 3.0 mmol), and stirred at room temperature. After complete dissolution, CBDA (0.55 g, 2.8 mmol) and NMP (5.0 g) were added to the chamber. The reaction was allowed to proceed for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A3 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 8,100 and a weight average molecular weight of 16,000.

(Production of liquid crystal alignment agent A4)

NMP (5.4 g) was added to the diamine [4] (1.37 g, 3.0 mmol), and stirred at room temperature. After complete dissolution, CBDA (0.55 g, 2.8 mmol) and NMP (5.4 g) were added to the chamber. The reaction was allowed to proceed for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A4 was obtained by stirring at room temperature for 5 hours. The polyamine had a number average molecular weight of 5,200 and a weight average molecular weight of 7,600.

(Production of liquid crystal alignment agent A5)

NMP (32.3 g) was added to the diamine [5] (7.06 g, 25.0 mmol), and stirred at room temperature. After complete dissolution, CBDA (4.51 g, 23.0 mmol) and NMP (33.2 g) were added to the chamber. The reaction was allowed to proceed for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (40 g), NMP (40.0 g) and BCS (20.0 g) were added, and the liquid crystal alignment agent A5 was obtained by stirring at room temperature for 5 hours. The polyamine has a number average molecular weight of 10,500 and a weight average molecular weight of 57,000.

(Production of Liquid Crystal Alignment Agent A6)

NMP (4.9 g) was added to the diamine [6] (1.18 g, 3.0 mmol), and stirred at room temperature. After complete dissolution, CBDA (0.53 g, 2.7 mmol) and NMP (4.9 g) were added to the chamber. The reaction was allowed to proceed for 10 hours to obtain a polyaminic acid solution. Adding NMP (10.0 g) to the polyamic acid solution (10 g) and BCS (5.0 g) was obtained by stirring at room temperature for 5 hours to obtain a liquid crystal alignment agent A6. The polyamino acid had a number average molecular weight of 8,800 and a weight average molecular weight of 35,000.

(Production of Liquid Crystal Alignment Agent A7)

NMP (5.6 g) was added to the diamine [7] (1.14 g, 4.5 mmol), and stirred at room temperature. After complete dissolution, CBDA (0.83 g, 4.2 mmol) and NMP (5.6 g) were added to the chamber. The reaction was allowed to proceed for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A7 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 13,800 and a weight average molecular weight of 35,500.

(Production of liquid crystal alignment agent A8)

NMP (33.3 g) was added to the diamine [8] (4.00 g, 10.0 mmol), and stirred at room temperature. After completely dissolved, CBDA (1.86 g, 9.5 mmol) was added, and the reaction was allowed to stand at room temperature for 10 hours. A polylysine solution was obtained. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A8 was obtained by stirring at room temperature for 5 hours. The polyamine had a number average molecular weight of 8,000 and a weight average molecular weight of 2,1200.

(Production of Liquid Crystal Alignment Agent A9)

NMP (24.6 g) was added to the diamine [9] (2.54 g, 10.0 mmol), stirred at room temperature, and CBDA (1.80 g, 9.2) was added after complete dissolution. Methyl), the reaction was allowed to proceed at room temperature for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A9 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 15,900 and a weight average molecular weight of 43,400.

(Production of Liquid Crystal Alignment Agent A10)

NMP (25.0 g) was added to the diamine [10] (2.54 g, 10.0 mmol), and stirred at room temperature. After completely dissolved, CBDA (1.86 g, 9.5 mmol) was added, and the reaction was allowed to stand at room temperature for 10 hours. A polylysine solution was obtained. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A10 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 4,300 and a weight average molecular weight of 7,800.

(Production of liquid crystal alignment agent A11)

NMP (25.0 g) was added to the diamine [11] (2.54 g, 10.0 mmol), and stirred at room temperature. After completely dissolved, CBDA (1.86 g, 9.5 mmol) was added, and the reaction was allowed to stand at room temperature for 10 hours. A polylysine solution was obtained. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A11 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 7,600 and a weight average molecular weight of 18,600.

(Production of Liquid Crystal Alignment Agent A12)

Add NMP (30.5g) to diamine [12] (3.52g, 10.0mmol) to After stirring at room temperature, CBDA (1.86 g, 9.5 mmol) was added after complete dissolution, and the reaction was allowed to proceed at room temperature for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A12 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 12,100 and a weight average molecular weight of 32,300.

(Production of liquid crystal alignment agent A13)

NMP (13.9 g) was added to the diamine [9] (2.54 g, 10.0 mmol), and stirred at room temperature. After complete dissolution, BODA (2.38 g, 9.5 mmol) and NMP (13.9 g) were added to 80. The reaction was allowed to proceed for 10 hours at ° C to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A13 was obtained by stirring at room temperature for 5 hours. The polyamino acid had a number average molecular weight of 6,200 and a weight average molecular weight of 14,900.

(Production of liquid crystal alignment agent A14)

NMP (14.2 g) was added to the diamine [10] (2.54 g, 10.0 mmol), and stirred at room temperature. After complete dissolution, BODA (2.45 g, 9.8 mmol) and NMP (14.2 g) were added to 80. The reaction was allowed to proceed for 10 hours at ° C to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A14 was obtained by stirring at room temperature for 5 hours. The polyamine had a number average molecular weight of 4,200 and a weight average molecular weight of 8,000.

(Production of Liquid Crystal Alignment Agent A15)

NMP (14.2 g) was added to the diamine [11] (2.54 g, 10.0 mmol), and stirred at room temperature. After complete dissolution, BODA (2.45 g, 9.8 mmol) and NMP (14.2 g) were added to 80. The reaction was allowed to proceed for 10 hours at ° C to obtain a polyaminic acid solution. To the polyamic acid solution (10 g), NMP (10.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment agent A15 was obtained by stirring at room temperature for 5 hours. The polyamine had a number average molecular weight of 5,700 and a weight average molecular weight of 12,100.

(Production of Liquid Crystal Alignment Agent B1)

NMP (22.0 g) was added to DA-1 (5.10 g, 14.0 mmol), and stirred at room temperature. After completely dissolved, CBDA (2.66 g, 13.6 mmol) and NMP (22.0 g) were added to room temperature. The reaction was carried out for 5 hours to obtain a polyaminic acid solution. To the polyamic acid solution (40 g), NMP (40.0 g) and BCS (20.0 g) were added, and the liquid crystal alignment agent B1 was obtained by stirring at room temperature for 5 hours. The polyamine has a number average molecular weight of 6,500 and a weight average molecular weight of 26,000.

<Production of liquid crystal cell> (Example 1)

The liquid crystal cell was produced in the order shown below using the liquid crystal alignment agent A1.

The substrate is a glass base having a size of 30 mm × 40 mm and a thickness of 0.7 mm. The plate and the ITO film are glass substrates which have been patterned and arranged with a comb-shaped pixel electrode. The pixel electrode has a comb-tooth shape in which the electrode elements having a "ㄑ shape" in which the central portion is curved are arranged in plural. The width of each electrode element in the short-side direction was 3 μm, and the interval between the electrode elements was 6 μm. Since the pixel electrodes forming the respective pixels are formed by arranging the electrode elements of the "ㄑ shape" in which the central portion is curved, the shape of each pixel is not rectangular, but is the same as that of the electrode elements. The part is a "ㄑ" shape that is curved and resembles a bold type. Then, each pixel is vertically divided by the central curved portion as a boundary, and has a first field on the upper side of the curved portion and a second field on the lower side. When the first field and the second field of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, when the alignment processing direction of the liquid crystal alignment film to be described later is used as a reference, the first field of the pixel is formed by the electrode element of the pixel electrode at an angle of +10° (clockwise), and the second field of the pixel is a pixel. The electrode elements of the electrodes are formed at an angle of -10° (counterclockwise). In other words, in the first field and the second field of each pixel, the applied voltage between the pixel electrode and the counter electrode reverses the direction of the induced liquid crystal in the substrate surface (In-Plane Switching). It is formed by the way of direction.

The liquid crystal alignment agent A1 was spin-coated on the prepared electrode-attached substrate. Subsequently, the film was dried on a hot plate at 90 ° C for 60 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Next, the substrate was placed on a hot plate at 240 ° C, and the liquid crystal alignment film was irradiated with ultraviolet rays of 313 nm at 20 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. In the same manner as described above, a liquid crystal alignment film A1 was used to form a liquid crystal alignment film, and an alignment treatment was performed on the glass substrate having no electrode having a height of 4 μm as a counter substrate.

A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on a liquid crystal alignment film of one of the substrates. Next, the other substrate is bonded so that the liquid crystal alignment film surface faces and the alignment direction becomes 0°, and then the sealing agent is cured to form an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal crystal having a structure of an IPS (In-Plane Switching) liquid crystal display device. Cell (liquid crystal cell for IPS type).

(Liquid alignment performance evaluation)

The alignment state of the liquid crystal cell for IPS type obtained above was observed by a polarizing microscope, and the person who had no alignment defect was judged as "good", and the person who had the alignment defect was judged as "poor". The results are shown in Table 1.

(afterimage evaluation)

The liquid crystal cell of the IPS type obtained above is placed between two polarizing plates arranged such that the polarizing axis is at a right angle, and the light source is placed in a state where no voltage is applied, and the arrangement angle of the liquid crystal cell is adjusted. The brightness of the transmitted light becomes the smallest. Then, the liquid crystal cell is rotated from the darkest angle of the second field of the pixel to the darkest angle of the first field, and the rotation angle (alignment azimuth angle) at this time is set as the initial alignment azimuth angle. Next, an alternating voltage of 8 V _PP was applied at a frequency of 30 Hz for 24 hours at room temperature. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were brought into a short state, and they were allowed to stand at room temperature for 1 hour. After being placed, the orientation azimuth angle is measured in the same manner, and the difference between the azimuth angles before and after the AC drive, that is, the alignment azimuth angle before the AC drive-AC drive azimuth angle is used as the Δ alignment azimuth angle ( °) and calculate. The results are shown in Table 1.

(Example 2)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A2 was used instead of the liquid crystal alignment agent A1.

(Example 3)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A3 was used instead of the liquid crystal alignment agent A1.

(Example 4)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A4 was used instead of the liquid crystal alignment agent A1.

(Example 5)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A5 was used instead of the liquid crystal alignment agent A1.

(Example 6)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A7 was used instead of the liquid crystal alignment agent A1.

(Example 7)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A8 was used instead of the liquid crystal alignment agent A1.

(Example 8)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A9 was used instead of the liquid crystal alignment agent A1.

(Example 9)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A10 was used instead of the liquid crystal alignment agent A1.

(Embodiment 10)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A11 was used instead of the liquid crystal alignment agent A1.

(Example 11)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A2 was used instead of the liquid crystal alignment agent A12.

(Embodiment 12)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A13 was used instead of the liquid crystal alignment agent A1.

(Example 13)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A14 was used instead of the liquid crystal alignment agent A1.

(Example 14)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent A15 was used instead of the liquid crystal alignment agent A1.

(Comparative Example 1)

The liquid crystal alignment performance evaluation and the afterimage evaluation were performed in the same manner as in Example 1 except that the liquid crystal alignment agent B1 was used instead of the liquid crystal alignment agent A1.

As a result, as shown in Table 1, the diamine represented by the above formula (1) was used as a raw material and polymerized in a polyimide group even under the conditions of a so-called low temperature and a short time at room temperature and 24 hours. In Examples 1 to 6 in which a specific photoreactive group was introduced into the main chain skeleton of the object, the difference in the azimuth angles before and after the AC driving was small as compared with Comparative Example 1, and the afterimage characteristics were significantly improved. Further, the liquid crystal alignment properties of Examples 1 to 6 were also good. Then, in Examples 12 to 11 in which various diamines were used, and in Examples 12 to 14 in which BODA was used as the acid dianhydride, the afterimage characteristics were remarkable as compared with Comparative Example 1 using the side chain type diamine. Promote and learn to show good Liquid crystal alignment performance. From these results, it was found that the photoreactive material using the main chain type diamine is superior to the liquid crystal alignment control force as compared with the side chain type diamine. Therefore, by using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film excellent in liquid crystal alignment property and afterimage characteristics can be obtained. Then, the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has excellent liquid crystal alignment properties and image sticking properties of the liquid crystal display device of the present invention, so that display defects and contrast reduction are less likely to occur, or A liquid crystal display device that is burned.

Claims (5)

A liquid crystal alignment agent comprising: a diamine component containing a diamine represented by the following formula (1) and a monocarboxylic acid dianhydride represented by the following formula (2): 1 mol% or more a polyimide obtained by using a tetracarboxylic acid component, a polymer obtained by imidating the polyimine precursor ruthenium, and at least one selected from the group consisting of polyimine and polyamine. (In the formula (1), X ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms (however, the non-adjacent -CH ₂ - of the alkylene group may be bonded via an ether bond, an ester bond or a guanamine bond) Substituting), X ² is -OCO-CH=CH- or -CH=CH-COO-, X ³ is a single bond, an alkylene group having a carbon number of 1 to 10 or a divalent benzene ring, and X ⁴ is a single bond, - OCO-CH=CH- or -CH=CH-COO-, X ⁵ is a single bond or an alkylene group having 1 to 6 carbon atoms (however, the non-adjacent -CH ₂ - of the alkylene group may be ether-bonded) , the ester bond or the amide bond is substituted); however, the formula (1) has one or more cinnamyl groups); (In the formula (2), Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and containing a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms. The liquid crystal alignment agent of claim 1, wherein the content of the tetracarboxylic dianhydride in the tetracarboxylic acid component is 5 mol% or more. The liquid crystal alignment agent of claim 1, wherein the content of the tetracarboxylic dianhydride in the tetracarboxylic acid component is 10 mol% or more. A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element characterized by comprising a liquid crystal alignment film of claim 4.