TWI457421B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having good electrical characteristics and excellent printability, the liquid crystal alignment film, and a liquid crystal display element having the same.

At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell is formed, which is formed of a polylysine, a polyimide, or the like on the surface of a substrate on which a transparent conductive film is provided. A liquid crystal alignment film is used as a substrate for a liquid crystal display element, and two substrates are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a unit cell of a sandwich structure, and liquid crystal molecules are formed. The long axis is continuously twisted 90 degrees from one substrate to the other. Further, an STN (Super Twisted Nematic) type liquid crystal display element and a vertical alignment type liquid crystal display element having higher contrast and smaller viewing angle dependence than the TN type liquid crystal display element have been developed. In the STN type liquid crystal display device, a liquid crystal in which a chiral agent as an optically active substance is blended in a nematic liquid crystal is used as a liquid crystal by using a state in which the long axis of the liquid crystal molecules is continuously twisted by 180 degrees or more between the substrates. And the resulting birefringence effect. In contrast, as described in Non-Patent Document 1 and Patent Document 1, a vertical alignment type liquid crystal display element called an MVA method in which protrusions are formed on ITO to control the alignment direction of liquid crystals has been proposed. The liquid crystal display element of the MVA type is excellent not only in viewing angle, contrast, and the like, but also in the process of forming the liquid crystal alignment film, and is not required to be subjected to rubbing treatment or the like, and is therefore excellent in process. As a liquid crystal alignment film which is applied to the TN, STN, and MVA systems, it is required that the afterglow erasing time of the liquid crystal display element is short. Further, as an alignment agent for forming the liquid crystal alignment films, it is required to have excellent printability in lithography.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-258605

[Non-Patent Document 1] "Liquid Crystal" Vol. 3 No. 2 117 (1999)

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film which maintains a voltage holding ratio while reducing accumulated charges, and which has excellent printability, and provides the liquid crystal alignment film. And a liquid crystal display element using the same.

Further objects and advantages of the invention will be apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are attained by a liquid crystal alignment agent characterized by containing a group consisting of a compound represented by the following formula (A) and a compound represented by the following formula (B). At least one compound (hereinafter, also referred to as a specific compound), (wherein R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group, R ₉ and R ₁₁ are an aromatic group, and R ₁₀ and R ₁₂ are each independently hydrogen. Atom, alkyl or glycidyl).

(wherein R ₁₃ and R ₁₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group, R ₁₅ and R ₁₇ are an aromatic group, and R ₁₆ and R ₁₈ are each independently a hydrogen atom. An alkyl group or a glycidyl group, and X represents a divalent organic group, -O- or -NH-).

Further, the liquid crystal alignment agent of the present invention preferably further contains at least one polymerization selected from the group consisting of polylysine represented by the following formula (I-1) and polyimine represented by (I-2). Things.

(wherein P ¹ is a tetravalent organic group, and Q ¹ is a divalent organic group), (wherein P ² is a tetravalent organic group, and Q ² is a divalent organic group).

According to the liquid crystal alignment agent of the present invention, it is possible to provide a liquid crystal alignment film capable of forming a liquid crystal alignment film while maintaining a voltage holding ratio while reducing accumulated charge, and having excellent printability, a liquid crystal alignment film thereof, and a liquid crystal display having the same element.

Hereinafter, the present invention will be described in more detail.

The liquid crystal alignment agent of the present invention is constituted by dissolving a specific compound and preferably at least one polymer (hereinafter also referred to as a specific polymer) selected from polyphthalic acid and polyimine in an organic solvent.

[Specific Compound 1]

The compound represented by the formula (A) is referred to as the specific compound 1.

In the formula (A), R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group. Specific examples of the alkyl group and the alkoxy group are an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group in the alkyl group and the alkoxy group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methyl-propyl group, and a 3-methyl-propyl group. Amyl, n-hexyl. Further, examples of the aromatic group of R ₁ to R ₈ include a phenyl group. R ₉ and R ₁₀ are an aromatic group, and specific examples thereof include a phenyl group and a naphthyl group. R ₁₀ and R ₁₂ each independently represent a hydrogen atom, an alkyl group or a glycidyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group.

In the formula (A), preferably R ₂ , R ₄ , R ₅ and R ₇ are hydrogen, and R ₁ , R ₃ , R ₆ and R ₈ are each independently hydrogen, methyl or ethyl, R ₉ , R ₁₁ is a phenyl group, and R ₁₀ and R ₁₂ are glycidyl groups.

Specific examples of the specific compound 1 include the following compounds.

Further, in the above compound, Me is a methyl group, and Et represents an ethyl group.

[specific compound 2]

The compound represented by the formula (B) is referred to as the specific compound 2.

In the formula (B), R ₁₃ and R ₁₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group. Specific examples of the alkyl group and the alkoxy group are an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group in the alkyl group and the alkoxy group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methyl-propyl group, and a 3-methyl-propyl group. Amyl, n-hexyl. Further, examples of the aromatic group of R ₁₃ and R ₁₄ include a phenyl group. R ₁₅ and R ₁₇ are an aromatic group, and specific examples thereof include a phenyl group and a naphthyl group. R ₁₆ and R ₁₈ each independently represent a hydrogen atom, an alkyl group or a glycidyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group.

X is a divalent organic group, -O- or -NH-. Preferred examples of the divalent organic group include -CH ₂ - or -CH ₂ CH ₂ -.

In the formula (B), R ₁₃ and R ₁₄ are preferably hydrogen, R ₁₅ and R ₁₇ are each a phenyl group, R ₁₆ and R ₁₈ are a glycidyl group, and X is -NH-, -CH ₂ - or -CH. ₂ CH ₂ -.

Specific examples of the specific compound 2 include the following compounds.

[polyglycolic acid]

<Tetracarboxylic acid dianhydride> As the tetracarboxylic dianhydride used in the synthesis of the polylysine, an alicyclic tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride can be used. Among them, an alicyclic tetracarboxylic acid dianhydride is preferred. Specific examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2-dimethyl-1,2,3,4. - cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2 -carboxynorbornane-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4 ,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-di Oxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4 ,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3 -dione, 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo[2.2.2]-oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5' -dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6- Tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10- a tetraketone, a compound represented by the following formulas (I) and (II),

(wherein R ¹ and R ³ represent a divalent organic group having an aromatic ring, R ² and R ⁴ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 present} may be the same or different).

Further, an aliphatic tetracarboxylic acid dianhydride such as butane tetracarboxylic acid dianhydride; pyromellitic dianhydride; 3,3',4,4'-benzophenonetetracarboxylic dianhydride; 3',4,4'-biphenylfluorene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic acid dianhydride, 3,3',4,4'-four Phenylnonane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsebacic anhydride, 4,4'-di (3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 2,2',3,3' -biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl) Phthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, two (three Phenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(benzene trimellitic anhydride), propylene glycol-bis(benzene trimellitic anhydride), 1,4-butanediol-two (benzene trimellitic anhydride), 1,6-hexanediol-bis(benzene trimellitic anhydride), 1,8-octanediol-bis(benzene trimellitic anhydride), 2,2-bis(4-hydroxyphenyl) An aromatic tetracarboxylic dianhydride such as a compound represented by the following formulas (1) to (4), propane-di(benzenetricarboxylic anhydride). They may be used alone or in combination of two or more.

Among the above tetracarboxylic dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl- are preferable from the viewpoint of being able to exhibit good liquid crystal alignment properties. 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2, 3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuranmethylidene)-3-methyl-3 - cyclohexene-1,2-dicarboxylic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3 ,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-six Hydrogen-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, bicyclo[ 2.2.2]-oct-7-ene-2 , 3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-di Ketone), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxyl 2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone In the compound represented by the above formula (I), the alicyclic tetracarboxylic dianhydride such as the compound represented by the following formulas (5) to (7) and the compound represented by the above formula (II) are the following formula (8). Examples of the alicyclic tetracarboxylic dianhydride such as the compound to be represented include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,3-dimethyl-1,2. 3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, cis-3,7-dibutylcyclooctane-1,5-diene -1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-diacid 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]- Furan-1,3-diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5 -(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxyl Norbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, and A compound represented by the formula (5).

Preferred tetracarboxylic acid dianhydrides other than the alicyclic tetracarboxylic dianhydride include tetrabutyltetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3'. 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and the like.

Among these tetracarboxylic dianhydrides, the alicyclic tetracarboxylic dianhydride is preferably 50 mol% or more based on the total tetracarboxylic dianhydride.

<Diamine> Examples of the diamine used in the synthesis of polylysine include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'. -diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 2,2'-dimethyl-4,4' -diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzamide, 4,4'-diaminodiphenyl Ether, 1,5-diaminonaphthalene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-di Aminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl) -1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4 - bis(4-aminophenoxy)benzene, 1,3- (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7- Diamino hydrazine, 9,9-dimethyl-2,7-diamino hydrazine, 9,9-bis(4-aminophenyl) fluorene, 4,4'-methyl-di(2- Chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'- Dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylphenylidene)diphenylamine, 4 , 4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-eight An aromatic diamine such as fluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine 4,4-Diaminoheptyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-anthracene Dimethyldiamine, tricyclo[6.2.1.0 ^2,7 ]- Aliphatic and alicyclic diamines such as undecylene dimethyl diamine, 4,4'-methyl bis(cyclohexylamine); 2,3-diaminopyridine, 2,6-diamino Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4- Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamine Base-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6 -phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4, 6-Diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3 -Dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl lactate, 3,8-diamino -6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole N-methyl-3,6-diamine The carbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, etc. have two first-order amine groups in the molecule and other than the amine group A diamine of a nitrogen atom; a diamine organooxane represented by the following formula (V). These diamines may be used alone or in combination of two or more.

(In the formula, R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁵ present may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20).

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'- are preferred. Diaminobiphenyl, 1,5-diaminonaphthalene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminopurine, 9,9- Dimethyl-2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9 - bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexa Fluoropropane, 4,4'-(p-phenylphenyldiisopropylidene)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-cyclohexane Diamine, 4,4'-methyl bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) Benzene, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N -Methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, and the like.

When the liquid crystal alignment agent of the present invention has a pretilt performance performance, it is preferred that some or all of Q ¹ and Q ² in the above formulas (I-1) and (I-2) are the following formula (Q-1). And at least one group represented by the following formula (Q-2). That is, a diamine having a group represented by the following formula (Q-1) or the following formula (Q-2) (hereinafter also referred to as "specific diamine") is used. They may be used alone or in combination of two or more.

(wherein X ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an extended aryl group, and R ⁶ is a carbon number of 10~ An alkyl group of 20, a monovalent organic group having an alicyclic skeleton of 4 to 40 carbon atoms or a monovalent organic group having a fluorine atom of 6 to 20 carbon atoms).

Wherein X ² is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an extended aryl group, and R ⁷ is a carbon number of 4~ a divalent organic group having an alicyclic skeleton of 40).

In the above formula (Q-1), the alkyl group having 10 to 20 carbon atoms represented by R ⁶ may, for example, be an n-decyl group, a n-dodecyl group, a n-pentadecyl group or a n-hexadecyl group. Octadecyl, n-icosyl, and the like. Further, R in the above formula (Q-1) and (Q-2) R in the above formula ^{6 7} carbon atoms represented by alicyclic skeleton having an organic group having 4 to 40, can be exemplified as having derived from a group of an alicyclic skeleton of a cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; a group having a steroid skeleton such as cholesterol or cholestyl alcohol; having norbornene or adamantane The group of the bridged ring skeleton, etc. Among them, a group having a steroid skeleton is particularly preferred. The organic group having the above alicyclic skeleton may also be a group substituted by a halogen atom, preferably a fluorine atom or a fluoroalkyl group, preferably a trifluoromethyl group.

In addition, the fluorine atom-containing group having 6 to 20 carbon atoms represented by R ^{6 in the} above formula (Q-1) may, for example, be a straight group having a carbon number of 6 or more, such as an n-hexyl group, an n-octyl group or a n-decyl group. An alkyl group; an alicyclic hydrocarbon group having 6 or more carbon atoms such as a cyclohexyl group or a cyclooctyl group; and a hydrogen atom such as an aromatic hydrocarbon group having 6 or more carbon atoms such as a phenyl group or a biphenyl group; a group substituted with a fluoroalkyl group such as an atom or a trifluoromethyl group.

Further, X ^{1 of the} above formula (Q-1) and X ² of the above formula (Q-2) are a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH- , -S- or aryl. Examples of the aryl group include a phenyl group, a tolyl group, a phenyl group, a naphthyl group and the like. Among them, a group represented by -O-, -COO-, or -OCO- is particularly preferred. Specific examples of the diamine having a group represented by the above formula (Q-1) include dodecyloxy-2,4-diaminobenzene and pentadecyloxy-2,4. -diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, a compound represented by the following formulas (9) to (13).

In addition, as a specific example of the diamine having a group represented by the above formula (Q-2), a diamine represented by the following formulas (14) to (16) is preferable.

Among them, particularly preferred are compounds represented by the above formulas (9), (11), (13), and (14).

The ratio of use of the specific diamine to the total amount of the diamine varies depending on the magnitude of the pretilt angle to be expressed, and in the case of the TN type or STN type liquid crystal display element, it is preferably 0 to 5 mol%. In the case of the vertical alignment type liquid crystal display element, it is preferably 5 to 100 mol%.

<Synthesis of Polylysine> The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably an acid anhydride group of the tetracarboxylic dianhydride with respect to 1 equivalent of the amine group of the diamine The ratio of 0.2 to 2 equivalents is more preferably a ratio of 0.3 to 1.2 equivalents.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent at a temperature of from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C.

Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N. - dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N, Aprotic solvents such as N-dimethylpropionamide, aprotic polar solvents such as dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-cresol, dimethyl A phenolic solvent such as phenol, phenol or halogenated phenol. Further, the amount (α) of the organic solvent is usually preferably an amount such that the total amount (β) of the tetracarboxylic acid dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (α + β) of the reaction solution.

Further, in the range in which the produced polyamine acid is not precipitated, an alcohol, a ketone, an ester, an ether or a halogenated hydrocarbon of a poor solvent of a polyglycolic acid may be used in combination in the above organic solvent. Classes, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butane. Alcohol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, acetic acid Ester, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol positive Ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, Trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diiso) Amyl ether and the like.

As described above, a reaction solution formed by dissolving polylysine can be obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled off under reduced pressure with an evaporator to obtain a polyamine. Further, the polyproline is re-dissolved in an organic solvent, and then the polypergic acid can be purified by performing a process of precipitating with a poor solvent once or several times or by vacuum distillation using an evaporator.

<Dehydration ring closure reaction> The polyimine in the liquid crystal alignment agent of the present invention can be synthesized by dehydration ring closure of a part or all of the above polyamic acid.

The dehydration ring closure of polylysine may be (i) by heating the poly-proline, or (ii) by dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed It is carried out by heating.

The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be completed. If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may decrease.

On the other hand, in the method of adding the dehydrating agent and the dehydration ring-closure catalyst to the polyamic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is, depending on the desired hydrazine imidization ratio, preferably 0.01 to 20 moles per 1 unit of repeating units of polymolecular acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0.01 to 10 mols per mol of the dehydrating agent used. The higher the amount of the above dehydrating agent and the dehydration ring-closure catalyst, the higher the yield of ruthenium. In addition, examples of the organic solvent used in the dehydration ring-closure reaction include an organic solvent exemplified as a solvent used in the synthesis of polylysine. Further, the reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. Further, the specific polymer obtained can be purified by subjecting the reaction solution thus obtained to the same operation as the method for producing polyamic acid.

The ratio of the repeating unit having a quinone ring in all the repeating units used in the present invention (hereinafter, also referred to as "deuterated imidization ratio") is 40 mol% or more, preferably 50 mol. More than 8% of the ear. By using a polymer having a ruthenium iodide ratio of 40 mol% or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a short afterimage erasing time can be obtained. The ruthenium amination rate can be obtained by the following method.

[Method for determination of oxime imidization ratio of ruthenium iodide polymer]

After the ruthenium iodide polymer was dried under reduced pressure at room temperature, it was dissolved in deuterated dimethyl hydrazine, and tetramethyl decane was used as a reference material to measure ¹ H-NMR at room temperature. The formula (ii) is obtained.

Ruthenium amination rate (%) = (1-A ¹ /A ² × α ) × 100 - (ii) A ¹ : Peak area of the proton derived from the NH group (10 ppm) A ² : derived from other protons peak area of α: the polymer precursor (polyamide acid), the relative ratio of the number of other protons to one proton of NH.

<End-Modified Polymer> The specific polymer used in the present invention may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating properties and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system in the synthesis of polyamic acid. Among them, as the monobasic acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber Anhydride, etc. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

[solution viscosity]

The polymer used in the alignment agent of the present invention preferably has a temperature of 20 to 800 mPa when it is a 10% solution. s viscosity, more preferably 30~500mPa. s viscosity.

Further, the solution viscosity (mPa.s) of the polymer was measured at 25 ° C using an E-type rotational viscometer using a specified solvent for a solution diluted to a specified solid content concentration.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention is usually constituted by dissolving the above specific compound in an organic solvent.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C.

The organic solvent constituting the liquid crystal alignment agent of the present invention is exemplified as a solvent for the synthesis reaction of polyglycine. Further, it is also possible to appropriately select and use as a poor solvent exemplified as a poor solvent which can be used in combination in the synthesis reaction of polyamic acid.

The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, so that a good film cannot be obtained. When the solid content concentration exceeds 10% by weight, the liquid crystal alignment film causes the coating film thickness to be too thick, so that a satisfactory liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases, and the coating characteristics are deteriorated.

Further, the range of the particularly preferable solid content concentration differs depending on the method used when the substrate is coated with the liquid crystal alignment agent. For example, when a spin coating method is used, it is particularly preferably in the range of 1.5 to 4.5% by weight. When using the printing method, the solid content concentration is in the range of 3 to 9% by weight, and therefore, the viscosity of the solution is preferably 12 to 50 mPa. The scope of s. When using the inkjet printing method, the solid content concentration is in the range of 1 to 5% by weight, and particularly preferably the solution viscosity is 3 to 15 mPa. The scope of s.

Examples of the organic solvent constituting the liquid crystal alignment agent of the present invention include 1-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene Alcohol ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylpropionamidine Amine, diisobutyl ketone (DIBK), isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. They may be used singly or in combination of two or more. Among them, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylpropyl The guanamine is particularly excellent in exhibiting good printability.

The liquid crystal alignment agent of the present invention may further contain a functional decane-containing compound or an epoxy compound from the viewpoint of improving the adhesion to the surface of the substrate within a range not impairing the physical properties of the object. As such a functional decane-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2- Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxyoxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-B Oxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylamine, 10- Trimethoxydecane-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6- Diazepine acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxy Decane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3-aminopropyltrimethoxydecane, N-di(oxyethyl)- 3-aminopropyltriethoxydecane, and the like. Examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetrahydration Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)amine Propyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-amine Methylcyclohexane and the like.

The compounding ratio of the functional decane-containing compound and the epoxy group-containing compound is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the polymer.

<Liquid Crystal Display Element> The liquid crystal display element obtained by the liquid crystal alignment agent of the present invention can be produced, for example, by the following method.

(1) Applying the liquid crystal alignment agent of the present invention to one side of a substrate provided with a patterned transparent conductive film by a lithography method, a spin coating method or an inkjet printing method, and then forming a coating layer by heating the coated surface membrane. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, alicyclic poly A transparent substrate made of plastic such as olefin. As the transparent conductive film provided on one surface of the substrate, a NESA film formed of tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and indium tin oxide (In ₂ O ₃ -SnO ₂ ) may be used. For the formation of these transparent conductive film patterns, such as an ITO film or the like, a photolithography method or a method of using a mask in advance is employed. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in advance. . After the application of the liquid crystal alignment agent, it is preferred to carry out preliminary heating (pre-baking) for the purpose of preventing the liquid of the applied alignment agent from flowing down. The pre-bake temperature is preferably from 30 to 300 ° C, more preferably from 40 to 200 ° C, and particularly preferably from 50 to 150 ° C. Thereafter, the solvent was completely removed to carry out a calcination process (post-bake) for the purpose of heat-imidating the polyglycolic acid. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. Thus, the liquid crystal alignment agent of the present invention containing polyglycine is removed by an organic solvent to form a liquid crystal alignment film as a liquid crystal alignment film. It is also possible to carry out dehydration ring closure by further heating to form a further yttrium-imided liquid crystal alignment film. The film thickness of the liquid crystal alignment film to be formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

(2) A polishing process in which the formed coating film surface is rubbed in a predetermined direction with a roll wrapped with a cloth formed of fibers such as nylon, rayon, or cotton. Thereby, the alignment of the liquid crystal molecules can be imparted to the coating film to form an alignment film. In the liquid crystal alignment film which is formed by the liquid crystal alignment agent of the present invention, the pretilt angle is partially changed by irradiating ultraviolet rays as shown in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Or, as shown in Japanese Laid-Open Patent Publication No. H5-107544, a resist film is partially formed on the surface of the liquid crystal alignment film which has been subjected to the rubbing treatment, and the resist is removed after being polished in a direction different from the previous grinding treatment ( The resist film is a process for changing the liquid crystal alignment of the liquid crystal alignment film, whereby the field of view characteristics of the liquid crystal display element can be improved.

(3) Two substrates in which the liquid crystal alignment film was formed as described above were produced, and the two substrates were arranged to face each other through the gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films were perpendicular or antiparallel to each other, and the two substrates were The peripheral portion is bonded with a sealant, and a liquid crystal is filled into the cell gap which is separated from the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, so that the polarizing direction is the same as or perpendicular to the polishing direction of the liquid crystal alignment film formed on one side of the substrate. , a liquid crystal display element is produced. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer may be used. Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and the trade names "C-15" and "CB-15" (manufactured by Merck & Co., Inc.) may be added. The chiral agent sold, etc. is used. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. In addition, as a polarizing plate to which the outer surface of the liquid crystal cell is bonded, a polarizing plate or a H which is obtained by sandwiching a polyvinyl alcohol and absorbing iodine and absorbing iodine, which is referred to as an H film, is sandwiched between a protective film of acetate. A polarizing plate made of the film itself.

Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer may be used.

Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and the trade names "C-15" and "CB-15" (manufactured by Merck & Co., Inc.) may be added. The chiral agent sold, etc. is used. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used.

In addition, as a polarizing plate to which the outer surface of the liquid crystal cell is bonded, a polarizing plate or a H which is obtained by sandwiching a polyvinyl alcohol and absorbing iodine and absorbing iodine, which is referred to as an H film, is sandwiched between a protective film of acetate. A polarizing plate made of the film itself.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples.

[Printability evaluation]

A 127 mm (D) × 127 mm (W) × 1.1 mm (H) glass substrate having an ITO film formed on the entire surface of one side was prepared, and the liquid crystal alignment agent obtained in the above experiment was a micropore filter having a pore diameter of 0.2 μm. After filtration, the liquid crystal alignment film coating printer (Angstromer S-40L, manufactured by Nippon Photo Printing Co., Ltd.) was applied onto the transparent electrode surface of the glass substrate. The film was dried by a hot plate-type preliminary preheater set to 80 ° C, and baked at 200 ° C for 60 minutes to form a liquid crystal alignment film on a glass substrate with an ITO film. The unevenness of the resulting alignment film was visually evaluated.

[Voltage retention rate]

In a 60 ° C environment, a voltage of 5 V was applied to the liquid crystal display element at a time interval of 167 msec, the voltage application time was 60 μsec, and then the voltage holding ratio from the voltage release to 167 msec was measured. The measuring device used VHR-1 manufactured by Dongyang Technology Co., Ltd.

[afterimage experiment]

A unit cell having an ITO electrode as shown in Fig. 1 was produced. At room temperature, a DC voltage of 6.0 V was applied to the electrode A for 24 hours, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the stress was released, a voltage of 0.1 to 5.0 V DC was applied to the electrodes A and B at a gradient of 0.1 V. The afterimage characteristics were judged by the difference in luminance between the electrodes A and B at the respective voltages. When the luminance difference is large, the afterimage characteristic is judged to be poor.

<Synthesis of Specific Compounds> Synthesis Example 1

To a 500 ml four-necked flask, 20 ml of toluene, 0.42 g (0.0018 mol) of palladium acetate (II) catalyst, and 1.5 g (0.0075 mol) of 3-stage butylphosphine were added under a nitrogen atmosphere, and after stirring for a few minutes, 4 was added dropwise. A solution of 29.3 g (0.094 mol) of 4'-dibromobiphenyl in 100 ml of toluene was further stirred for 10 minutes.

Next, 200 ml of a toluene solution of aniline 18.3 g (0.196 mol) was added, and then 15.86 g (0.165 mol) of sodium butoxide sodium was added thereto, and the mixture was heated under reflux for 4 hours to cause a reaction. After the reaction was completed, water was added to the vessel and extracted with diethyl ether. After dehydration with sodium sulfate, sodium sulfate was filtered off and the solvent was removed by rotary evaporator. The crude product was purified by hydrazine column chromatography to give the specific compound (A-1).

Synthesis Example 2

To a 500 ml four-necked flask, 20 ml of toluene, 0.42 g (0.0018 mol) of palladium acetate (II) catalyst, and 1.5 g (0.0075 mol) of 3-stage butylphosphine were added under a nitrogen atmosphere, and after stirring for a few minutes, 2 was added dropwise. A solution of 30.4 g (0.094 mol) of 7-dibromofluorene in 100 ml of toluene was further stirred for 10 minutes. Next, 200 ml of a toluene solution of aniline 18.3 g (0.196 mol) was added, and then 15.86 g (0.165 mol) of sodium butoxide sodium was added thereto, and the mixture was heated under reflux for 4 hours to cause a reaction. After the reaction was completed, water was added to the vessel and extracted with diethyl ether. After dehydration with sodium sulfate, sodium sulfate was filtered off and the solvent was removed by rotary evaporator. The crude product was purified by hydrazine column chromatography to give the specific compound (B-1).

Synthesis Example 3

The compound (A-2) was obtained by the same procedure as in Synthesis Example 1 except that the aniline used in Synthesis Example 1 was replaced with 4-n-propylaniline.

Synthesis Example 4

The compound (B-2) was obtained by the same procedure as in Synthesis Example 2 except that the aniline used in Synthesis Example 2 was replaced with 4-n-propylaniline.

Synthesis Example 5

3.36 g (0.01 mol) of a specific compound (A-1), 100 ml of THF, and 1.56 g (0.04 mol) of sodium amination were mixed in a 500 ml three-necked flask. The solution was heated to reflux for 2 hours. The reaction solution was cooled, and 3.42 ml (0.04 mol) of epibromohydrin was added dropwise. After the completion of the dropwise addition, the mixture was heated to 80 ° C and stirred for 6 hours. After removing the THF by a rotary evaporator, chloroform was added. The solution was washed with a 10% aqueous hydrochloric acid solution and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and filtered and evaporated. The solvent was distilled off from the organic layer. Further, it was purified by oxidative column chromatography to give a specific compound (A-3). The specific compound (A-3) contains two kinds of products as shown in the above formula.

Synthesis Example 6

Compound (B-1) 17.4 g (0.05 mol), DMSO 120 ml, and potassium carbonate 16.59 g (0.12 mol) were mixed in a 500 ml three-necked flask. After the solution was cooled in an ice bath, 160 ml of a solution of 16.44 g (0.12 mol) of oxidized bromopropane in DMSO was added dropwise. After the completion of the dropwise addition, the mixture was returned to room temperature, and stirring was continued for 48 hours. The reaction solution was filtered, and the filtrate was concentrated by a rotary evaporator, and the excess of the epibromo-bromopropane was removed by a vacuum pump. The obtained crude product was diluted with 200 ml of toluene, and the solution was washed 4 times with 100 ml of distilled water. After adding sodium sulfate and allowing to stand for 1 night, sodium sulfate was filtered off, and the solvent was removed by a rotary evaporator. The obtained crude product was purified by ruthenium oxide column chromatography to give a specific compound (B-3). B-3 contains two kinds of products as shown in the above formula.

Synthesis Example 7

The specific compound (A-4) was obtained by the same procedure as in Synthesis Example 5 except that the specific compound (A-1) used in Synthesis Example 5 was replaced by (A-2). A-4 contains two products as shown above.

Synthesis Example 8

The specific compound (B-4) was obtained by the same procedure as in Synthesis Example 6 except that the specific compound (B-1) used in Synthesis Example 6 was replaced by (B-2). B-4 contains two kinds of products as shown in the above formula.

Polyimine synthesis Example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride 112 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydrogen -8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione 157 g (0.50 mol), P-phenylenediamine as a diamine compound 96 g (0.89 mol), 3,3'-(tetramethyldioxane-1,3-diyl)di(propylamine) 25 g (0.10 mol) and 3 , 6-bis(4-aminobenzimidyloxy)cholestane 13g (0.020 mol), n-octadecylamine as a monoamine 8.1 g (0.030 mol) dissolved in 960 g of N-methyl- The 2-pyrrolidone was allowed to react at 60 ° C for 6 hours. The obtained polyaminic acid solution was taken out in small portions, NMP was added, and the viscosity was measured at a solid concentration of 10%, which was 60 mPa. s. Next, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 396 g of pyrrole and 409 g of acetic acid were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. After the hydrazine imidization reaction, the solvent in the system is subjected to solvent replacement with a new γ-butyrolactone (in this operation, pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain about 2000g solid concentration 15wt%, solid concentration 6.0% (γ-butyrolactone solution) solution viscosity 16mPa. s, a ruthenium iodide having a ruthenium iodide ratio of about 95% (as a "polyimine (a-1)") solution.

Polyimine synthesis example 2 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, p-phenylenediamine 108 g (1.0 mol) as a diamine compound And 7.8 g (0.015 mol) of 3,5-diaminobenzoic acid cholesteryl ester were dissolved in 3039 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 6 hours to obtain a solution. The viscosity is about 260mPa. s polylysine solution. Next, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 396 g of pyridine and 306 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. After the hydrazine imidization reaction, the solvent in the system is subjected to solvent replacement with a new γ-butyrolactone (in this operation, pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain about 3000g solid concentration 9.0wt%, solid concentration of 5.0% (γ-butyrolactone solution) solution viscosity 72mPa. s, a solution of a ruthenium iodide having a ruthenium iodide ratio of about 89% as a "ruthenium iodide polymer (a-2)").

Polylysine Synthesis Example 1 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride as 2,2'-dimethyl diamine compound Base group 4,4'-diaminobiphenyl 212 g (1.0 mol) was dissolved in 370 g of N-methyl-2-pyrrolidone and 3300 g of γ-butyrolactone, and allowed to react at 40 ° C for 3 hours to obtain about 3700 g. The solution viscosity is 160mPa. Poly lysine (as a "polyamido acid (b-1)") solution.

Polylysine Synthesis Example 2 95 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as a tetracarboxylic dianhydride, and 109 g (0.50 mol) of pyromellitic dianhydride. 2,7-diaminopurine 196 g (1.0 mol) as a diamine compound was dissolved in 230 g of N-methyl-2-pyrrolidone and 2060 g of γ-butyrolactone, and after reacting at 40 ° C for 3 hours, Add 1350g γ-butyrolactone to obtain a solution viscosity of about 3600g with a solid concentration of 10% and a solution viscosity of 125mPa. Poly lysine of s (as a "polyamido acid (b-2)") solution.

Example 1 Polyimine (a-1) prepared in Polyimine Synthesis Example 1 and Polylysine (b-1) prepared in Polyamine Synthesis Example 1 as Polyimine : Polyglycine = 20:80 (weight ratio) dissolved in γ-butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 71/17/12), relative to 100 weight 2 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and 10 parts by weight of a specific compound (A) is added to 100 parts by weight of the polymer. -1), a solution having a solid concentration of 3.5% by weight and a solution of 6.0% by weight were prepared. After each solution was thoroughly stirred, it was filtered with a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention.

A solution having a solid concentration of 3.5% by weight in the above liquid crystal alignment agent was applied onto a transparent conductive film formed of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spin coater (rotation speed: 2500 rpm, coating) Time: 1 minute), dried at 200 ° C for 1 hour to form a film having a dry film thickness of 0.08 μm. The coating film was subjected to a grinding treatment using a sanding machine equipped with a roll of a woven fabric made of rayon, at a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 0.4 mm. Ultrasonic water was washed in ultrapure water for 1 minute and dried in a 100 ° C clean oven for 10 minutes. Then, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhesive to which alumina balls having a diameter of 5.5 μm are applied is applied, and then The liquid crystal alignment film surface is relatively recombined and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) was filled between the substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to form a liquid crystal display element of the present invention. The evaluation of the voltage holding ratio and the afterimage of the obtained liquid crystal display element was carried out in accordance with the method described above.

The printability evaluation was performed by the method as described above using the solution having a solid content concentration of 6.0% by weight.

Examples 2 to 8 were carried out in the same manner as in Example 1 except that the polyamine imine, polylysine, and the specific compound were used as shown in Table 1.

Example 9 The polyimine (a-2) obtained in the polyimine synthesis example 2 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 50/50), as opposed to 2 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane is added to 100 parts by weight of the polymer, and 10 parts by weight of the specific component is added with respect to 100 parts by weight of the polymer. Compound (A-1) was prepared as a solution having a solid concentration of 3.5% by weight and a solution of 6.0% by weight. After each solution was thoroughly stirred, it was filtered with a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. The method for producing a liquid crystal display element, the method for evaluating a liquid crystal display device, and the method for evaluating the printability of an alignment agent were carried out in the same manner as in Example 1.

Examples 10 to 12 were carried out in the same manner as in Example 9 except that the specific compounds were used as shown in Table 1.

Comparative Examples 1 and 2 were carried out in the same manner as in Example 1 except that the materials shown in Table 1 were used for the polyimine and the polyamic acid, and the specific compound was not added.

Comparative Example 3 was carried out in the same manner as in Example 9 except that no specific compound was added.

Comparative Examples 4 to 5 except for the polyimine and polylysine, the materials shown in Table 1 were used, and N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (compound) was used. Z) was carried out in the same manner as in Example 1 except that the specific compound was used.

Comparative Example 6 was carried out in the same manner as in Example 9 except that N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (Compound Z) was used instead of the specific compound.

Fig. 1 is an explanatory view of a unit cell produced by an afterimage experiment.

Claims (5)

A liquid crystal alignment agent comprising at least one compound selected from the group consisting of a compound represented by the following formula (A) and a compound represented by the following formula (B), (wherein R ₁ to R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₉ and R ₁₁ are a phenyl group or a naphthyl group, and R ₁₀ and R ₁₂ are glycidyl groups), (wherein R ₁₃ and R ₁₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group, R ₁₅ and R ₁₇ are a phenyl group or a naphthyl group, and R ₁₆ and R ₁₈ are each independently hydrogen. An atom or a glycidyl group, and X represents a divalent -CH ₂ -, -CH ₂ CH ₂ -, -O- or -NH-). The liquid crystal alignment agent of the first aspect of the invention, which further comprises a group consisting of polylysine represented by the following formula (I-1) and polyimine represented by the following formula (I-2) At least one polymer, In the formula (I-1) and the formula (I-2), P ¹ and P ² are tetravalent organic groups derived from the following: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride 1,2-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride , 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylate Acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclic Hexyltetracarboxylic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxyl ring Amyl acetal dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1, 3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo -3 -furyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3 ,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan -1,3-dione, 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo[2.2.2]-octyl -7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2 ',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3, 5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5, 8,10-tetraketone, a compound represented by the following formulas (I) and (II): (wherein R ¹ and R ³ represent a divalent organic group having an aromatic ring, R ² and R ⁴ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 present} may be the same or different) Butane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic acid Diacid anhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Anhydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3 , 4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy Diphenyl sebacic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene Phthalic anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, diphenylphthalate Oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, di(triphenylene) Terephthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(benzene trimellitic anhydride), Propylene glycol-bis(benzene trimellitic anhydride), 1,4-butanediol-bis(benzene trimellitic anhydride), 1,6-hexanediol-bis(benzene trimellitic anhydride), 1,8-octanediol- Bis(benzene trimellitic anhydride), 2,2-bis(4-hydroxyphenyl)propane-bis(benzene trimellitic anhydride), one or two selected from the compounds represented by the following formulas (1) to (4) More than the above tetracarboxylic dianhydride, Q ¹ and Q ² are divalent organic groups derived from the following: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 2,2'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzimidil, 4,4'-diaminodiphenyl ether, 1,5-Diaminonaphthalene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diamino Biphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1 , 3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-Diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)benzene Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-di (4-Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-di (4 -aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9- Methyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methyl-bis(2-chloroaniline), 2,2',5 , 5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene) Isopropyl)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2 , 2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 1,1-isophenyl Dimethylamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4 -diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene quinone dimethylenediamine, tricyclo[6.2.1.0 ^{2, 7} ]-undecene dimethyldiamine, 4,4'-methyl bis(cyclohexylamine), 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4- Diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2, 4-diamino-6-di Methylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy-1,3,5- Triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2, 4-Diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine , 2,4-Diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino- 1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diamine Pyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole , N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, 1 selected from the group consisting of the diamine organooxane represented by the following formula (V) Species or more than two kinds of diamines, (In the formula, R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁵ present may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20). The liquid crystal alignment agent of the second aspect of the invention, wherein the polyamic acid represented by the above formula (I-1) and the tetracarboxylic acid dianhydride used in the synthesis of the polyimine represented by the above formula (I-2) comprise 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal alignment film which is used in items 1 to 3 of the patent application scope Any one of liquid crystal alignment agents. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 4 of the patent application.