TWI655245B - Liquid crystal aligning agent, liquid crystal aligning film and method for manufacturing the same, liquid crystal display device - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a method for producing the same, a liquid crystal display element, a polymer, and a compound. In the present invention, the polymer (P) having a partial structure represented by the following formula (1) in the main chain is contained in the liquid crystal alignment agent.

*-X ¹ -Y ¹ -X ¹ -* (1) (X ¹ is a divalent organic group, and Y ¹ is a divalent linking group or a single bond; wherein at least one of the two X ¹ is a divalent aromatic In the case of a heterocyclic group, when only one of the two X ¹ is a divalent aromatic heterocyclic group, Y ¹ is a divalent linking group having one or more nitrogen atoms, and two X ^{1 are} bonded to Y. on the same or a different nitrogen atom in ^1; 2 X ¹ may be identical or different; "*" represents a bonding bond)

Description

Liquid crystal alignment agent, liquid crystal alignment film, manufacturing method thereof, liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a method for producing the same, and a liquid crystal display element.

In recent years, liquid crystal display elements have been used not only for display terminals such as personal computers as in the past, but also for various applications such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, and information displays. In addition, in order to satisfy such a demand, various liquid crystal alignment agents are provided in order to satisfy such a demand (see, for example, Patent Document 1 to Patent Document 3).

Patent Document 1 to Patent Document 3 disclose a polymer component which is a liquid crystal alignment agent using a polyamine obtained by reacting a diamine having a pyridazine ring with a tetracarboxylic dianhydride or a derivative thereof. Specifically, Patent Document 1 discloses that an aromatic diamine having a partial structure of "-benzene ring-pyridazine ring-benzene ring-" is used for a single In the patent document 3, a diamine having a partial structure of "-alkylene chain-pyridazine ring-alkylene chain-" is used for a monomer. By using the diamine, it is attempted to obtain a liquid crystal alignment film having an appropriate ion density and long-term reliability. Further, Patent Document 2 discloses that a polyimine obtained by using a diamine having a pyridazine ring for polymerization of a monomer is contained in a liquid crystal alignment agent to improve heat resistance of the liquid crystal alignment film and Charged voltage leakage.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-175684

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-2501

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-28223

In order to improve the display quality, various characteristics are required for the liquid crystal alignment film. Examples of the liquid crystal alignment, the difficulty of generating an afterimage (after-image characteristics), and reliability are examples of important characteristics. In particular, reliability, with the versatility of liquid crystal display elements, is assumed to be used in a severe environment such as long-term continuous driving or thermal stress, optical stress, etc., in order to be able to withstand use in the harsh environment, the reliability Very important. In order to achieve further improvement in quality, liquid crystal display elements are required to further improve these various characteristics.

The present invention has been made in view of the above problems, and the main object is to provide a A liquid crystal alignment agent can form a coating film having good liquid crystal alignment properties, and can obtain a liquid crystal display element having excellent reliability and afterimage characteristics.

The inventors of the present invention conducted active research in order to achieve the problems of the prior art as described above, and as a result, found that a polymer component containing a polymer having a specific partial structure containing a nitrogen atom in the main chain as a liquid crystal alignment agent was found. The problem can be solved, and the present invention has been completed. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, method for producing a liquid crystal alignment film, and liquid crystal display element.

One aspect of the present invention provides a liquid crystal alignment agent comprising a polymer (P) having a partial structure represented by the following formula (1) in a main chain.

[Chemical Formula 1] *-X ¹ -Y ¹ -X ¹ -* (1) (In the formula (1), X ¹ is a divalent organic group, and Y ¹ is a divalent linking group or a single bond; wherein, 2 X At least one of ¹ is a divalent aromatic heterocyclic group, and when only one of the two X ¹ is a divalent aromatic heterocyclic group, Y ¹ is a divalent linking group having one or more nitrogen atoms. And 2 X ¹ bonds are on the same or different nitrogen atoms in Y ¹ ; 2 X ¹ may be the same or different; "*" means bonding hand)

One aspect of the present invention provides a method for producing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent onto a substrate to form a coating film, and irradiating the coating film with light to impart liquid crystal alignment ability And a method for producing a liquid crystal alignment film, comprising: forming a coating using the liquid crystal alignment agent a step of filming; and a step of subjecting the coating film to a rubbing treatment to impart alignment ability to the liquid crystal. Further, the present invention provides a liquid crystal alignment film formed of the liquid crystal alignment agent and a liquid crystal display element including the liquid crystal alignment film.

Another aspect of the present invention provides a polymer which is at least one selected from the group consisting of polylysine, polyphthalate, and polyimine, and has the formula in a main chain (1) Part of the structure indicated.

Further, another aspect of the present invention provides a compound represented by the following formula (3).

(In the formula (3), X ¹ is a divalent organic group, wherein at least one of the two X ¹ is a divalent aromatic heterocyclic group; Z ¹ is a primary amino group or the following formula (z-1)

(In the formula (z-1), "*" represents a group represented by a bond of X ¹ ); R ¹ is a single bond, an alkanediyl group having a carbon number of 1 to 6 or a cyclohexyl group, and R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or two R ² groups bonded to each other to form a divalent alicyclic heterocyclic group having 2 to 10 carbon atoms together with 2 nitrogen atoms and R ¹ ; 2 X ¹ Can be the same or different, 2 R ² can be the same or different; p is 0 or 1)

According to the liquid crystal alignment agent of the present invention, a coating film having a good liquid crystal alignment property can be formed by including a polymer having a specific structure in at least a part of the polymer component, and a liquid crystal display element having excellent reliability and afterimage characteristics can be obtained. .

Hereinafter, each component contained in the liquid crystal alignment agent of the present invention and other components arbitrarily formulated as needed will be described.

<Polymer (P)>

The liquid crystal alignment agent of the present invention contains a polymer (P) having a structure represented by the following formula (1) in the main chain as at least one component of the polymer component.

[Chem. 4] *-X ¹ -Y ¹ -X ¹ -* (1) (In the formula (1), X ¹ is a divalent organic group, and Y ¹ is a divalent linking group or a single bond; wherein, 2 X At least one of ¹ is a divalent aromatic heterocyclic group, and when only one of the two X ¹ is a divalent aromatic heterocyclic group, Y ¹ is a divalent linking group having one or more nitrogen atoms. And 2 X ¹ bonds are on the same or different nitrogen atoms in Y ¹ ; 2 X ¹ may be the same or different; "*" means bond key)

The divalent aromatic heterocyclic group of X ¹ in the formula (1) is a group obtained by removing two hydrogen atoms from the atom constituting the ring of the aromatic hetero ring, and a substituent may be introduced into the ring portion. . The ring portion of X ¹ is preferably an aromatic hetero ring containing a nitrogen atom, and specific examples thereof include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, anthracene, benzimidazole, Anthracene, quinoline, isoquinoline, naphthyridine, quinoxaline, pyridazine, triazine, azide, diazonium, acridine, phenazine, phenanthroline, oxazole, thiazole, oxazole, thiadiazole , benzothiazole, phenothiazine, oxadiazole and the like.

Examples of the substituent which can be introduced into the ring portion of the aromatic heterocyclic group of X ¹ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; and a chain or a branch such as a methyl group, an ethyl group or a propyl group; An alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group.

The ring of the aromatic heterocyclic group of the X ¹ in the aromatic heterocyclic ring, from the viewpoints of easiness of synthesis of the monomer, reduction in image sticking of the liquid crystal display element, and reliability The backbone is preferably pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine or triazine, more preferably pyridine, pyrimidine or pyrazine. The two bonding bonds in X ¹ are preferably at the 1,4-position relative to the other groups.

Examples of the divalent organic group of X ¹ include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Among these, a divalent aromatic hydrocarbon group is preferable from the viewpoint of the reliability of the liquid crystal display element and the effect of improving the afterimage characteristics, and specific examples thereof include a phenylene group and a biphenylene group. , stretching naphthyl and the like. It is preferably a phenyl group or a biphenyl group.

The two X ¹ in the formula (1) are preferably both a divalent aromatic heterocyclic group in terms of a reduction in image sticking of the liquid crystal display element and a high effect of improving the reliability.

Specific examples of the divalent linking group of Y ¹ include, for example, -O-, -CO-, -COO-, -NR ^a -, -CONR ^a -, -NR ^a CONR ^a - (wherein R ^a is a hydrogen atom Or a divalent functional group such as a hydrocarbon group having 1 to 6 carbon atoms, -N=N-, -COS- or -S-; a divalent chain such as a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; a hydrocarbon group; a group obtained by substituting at least one methylene group in a divalent hydrocarbon group with the divalent functional group; a divalent group having a hetero ring;

Here, the "chain hydrocarbon group" in the present specification means a linear hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain but are composed only of a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. Among them, it is not necessarily required to be composed only of the structure of the alicyclic hydrocarbon, and also includes a hydrocarbon group having a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessarily required to be composed only of an aromatic ring structure, and a structure of a chain structure or an alicyclic hydrocarbon may be contained in a part thereof.

The divalent linking group of Y ¹ is preferably a group having at least one nitrogen atom from the viewpoint of reducing image sticking and reliability of the liquid crystal display element, and more preferably a group having two or more nitrogen atoms. The upper limit of the number of nitrogen atoms which Y ¹ has is not particularly limited, but is preferably 4 or less, and more preferably 3 or less.

When Y ¹ is a divalent organic group having one or more nitrogen atoms, it is preferred that two X ¹ are bonded to each of the nitrogen atoms in Y ¹ . In the case where Y ¹ is a divalent linking group having two or more nitrogen atoms, two X ¹ may be bonded to the same nitrogen atom in Y ¹ or may be bonded to a different nitrogen atom, preferably a bond. On different nitrogen atoms in Y ¹ . Further, when only one of the two X ¹ is a divalent aromatic heterocyclic group, Y ^{1 is} a divalent linking group having one or more nitrogen atoms. In this case, the two X ¹ bonds in the formula (1) are bonded to the same or different nitrogen atoms in Y ¹ .

Specific examples of the Y ^{1 which} is particularly preferable are, for example, a group represented by the following formula (Y-1).

(In the formula (Y-1), R ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms or a cyclohexyl group, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or 2 R ² are mutually Bonding together with two nitrogen atoms and R ¹ to form a divalent alicyclic heterocyclic group having 2 to 10 carbon atoms; two R ^{2 's} may be the same or different; p is 0 or 1; "*" means X ¹ key button)

Examples of the alkanediyl group having 1 to 6 carbon atoms of R ¹ in the formula (Y-1) include a methylene group, an exoethyl group, a propylene group, a butyl group, a pentane group, a hexyl group, and the like. These alkanediyl groups may be linear or branched. R ¹ is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. In the case where R ¹ is a cyclohexylene group, it is preferably a 1,4-cyclohexylene group.

Examples of the alkyl group having 1 to 6 carbon atoms of R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. These alkyl groups may be linear or branched. The alkyl group preferably has a carbon number of 1 to 4, and more preferably has a carbon number of 1 to 3.

When p is 0 or 1, from the viewpoint of improving the reliability and afterimage characteristics of the liquid crystal display element, p=1 is preferable.

In the case of p=1, there are two R ² in the formula (Y-1). The divalent alicyclic heterocyclic group formed by bonding these two R ^{2 to} each other is a group obtained by removing two hydrogen atoms from the atom constituting the ring of the alicyclic heterocyclic ring, specifically, It is represented by the following formula (Y-1-1).

(In the formula (Y-1-1), R ¹¹ is a monovalent substituent, k is an integer of 0 to (a+b); a and b are integers of 0 or more satisfying a+b≧2; "*" Indicates the key combination)

R ^{11 of} the formula (Y-1-1) may, for example, be a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. k is preferably zero.

The alicyclic heterocyclic group represented by the formula (Y-1-1) preferably has a ring number of 5 to 12, and more preferably 5 to 7. The 1,4-pyridazinediyl group is particularly preferable in that the relaxation rate of the accumulated electric charge is fast and the effect of reducing the afterimage is high.

The structure represented by the formula (1) is preferably a structure represented by the following formula (2).

(In the formula (2), X ¹ is a divalent organic group, wherein at least one of the two X ¹ is a divalent aromatic heterocyclic group; and R ¹ , R ² and p are the same as the formula (Y-1) The meaning is the same; "*" means the key button)

Preferable specific examples of the structure represented by the above formula (1) include the following formulas (2-1-1) to (2-1-8) and (2-2-1) to (2). -2-5), Formula (2-3-1)~Formula (2-3-3), Formula (2-4-1)~Formula (2-4-5), Formula (2-5-1) Structures and the like represented by the formulas (2-5-6) and (2-6-1), respectively.

(where "*" means the keying key).

[Chemistry 9] (where "*" means the keying key).

The main chain of the polymer (P) may, for example, be a skeleton comprising polylysine, polyimine, polyphthalate, polyester, polyamine or the like. Further, the "main chain" of the polymer in the present specification is a structure formed by reversibly bonding one or two or more kinds of monomers, and means the longest "dry" part of the polymer. Therefore, the phrase "having a partial structure represented by the above formula (1) in the main chain" means that the structure constitutes a part of the "dry" of the polymer. In the polymer (P), it is not excluded that the structure represented by the formula (1) is also present in a portion other than the main chain, for example, a side chain (a portion branched from the "dry" of the polymer). Case.

The polymer (P) can be obtained, for example, by a method in which a compound having the structure represented by the formula (1) is used for polymerization of a monomer.

The polymer (P) can be used by appropriately selecting one or more selected from the group consisting of these. Among them, it is preferable that the polymer (P) is at least one selected from the group consisting of polyproline, polyimine, and polyphthalate.

[polyaminic acid (P)]

In the case where the polymer (P) is poly-proline (hereinafter also referred to as "poly-proline (P)"), the poly-proline (P) can be, for example, made tetracarboxylic dianhydride Obtained by reaction with a diamine. Specifically, for example, it can be obtained by the following method: (i) using a tetracarboxylic dianhydride having a partial structure represented by the above formula (1) (hereinafter also referred to as "specific tetracarboxylic dianhydride") for a method of performing polymerization by using a monomer; (ii) a method of using a diamine having a partial structure represented by the formula (1) (hereinafter also referred to as "specific diamine") for polymerization; (iii) A method in which a specific tetracarboxylic dianhydride and the specific diamine are used for a monomer to carry out polymerization.

[tetracarboxylic dianhydride]

(specific tetracarboxylic dianhydride)

The specific tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) is, for example, a compound represented by the following formula (3-1b).

(In the formula (3-1b), X ¹ and Y ^{1 have} the same meanings as in the above formula (1))

X with respect to the formula (3-1b) is ¹ and Y ^1, respectively Description of the formula X (1) is ¹ and Y ^1.

Specific examples of the compound represented by the formula (3-1b) include compounds represented by the following formulas (4-1) to (4-8), and the like. Further, the specific tetracarboxylic dianhydride may be used alone or in combination of two or more.

The specific tetracarboxylic dianhydride is preferably such that Y ¹ in the formula (3-1b) is a group represented by the formula (Y-1), specifically, the following formula (3-B) The compound represented.

(In the formula (3-B), the meanings of R ¹ , R ² and p are the same as those of the formula (Y-1), and the meaning of X ^{1 is} the same as the formula (2))

Regarding X ¹ of the formula (3-B), the description of X ¹ of the formula (1) can be applied. Further, with respect to R ¹ and R ^2, each R may be the use of formula (Y-1) ¹ and R ² is described. p is preferably 1.

Specific examples of the compound represented by the formula (3-B) include, for example, the above formula. (4-1) - a compound represented by the formula (4-4), the formula (4-7), and the formula (4-8), and the like.

Further, the compound represented by the formula (3-B) can be synthesized by appropriately combining a common method of organic chemistry. When one of the examples, a diamine (a compound represented by the following formula (3-A)) having a structure represented by the formula (2) and a reaction with a carboxyl group-containing halide can be synthesized. The tetracarboxylic acid of the structure represented by the formula (2) is then subjected to intramolecular dehydration condensation to obtain the compound represented by the formula (3-B).

(other tetracarboxylic dianhydride)

The tetracarboxylic dianhydride used for the synthesis of the polymer (P) may be used singly as the specific tetracarboxylic dianhydride, or may be used together with a specific tetracarboxylic dianhydride.

Examples of the other tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic monocarboxylic dianhydride: 1,2,3,4-butanetetracarboxylic dianhydride; and alicyclic tetracarboxylic dianhydride. : 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro 8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[ 3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6- Anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ] Monoalkane-3,5,8,10-tetraketone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, p-phenylenebis (p-phenylenebis) Trimellitic acid monoester anhydride)), etc.; the aromatic tetracarboxylic dianhydride may, for example, be pyromellitic dianhydride or the like; Patent Laid-Open Publication No. 2010-97188 described tetracarboxylic dianhydride and the like. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

The preferred use ratio of the specific tetracarboxylic dianhydride varies depending on the method of synthesizing polyglycolic acid (P). For example, in the case of the method (i), it is preferred to set the use ratio of the specific tetracarboxylic dianhydride to 5 with respect to the total amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P). More than or equal to mol%, more preferably 10 mol% or more, and particularly preferably 20 mol% or more. The upper limit of the use ratio is not particularly limited, and can be appropriately selected within a range of 100 mol% or less.

[diamine]

(specific diamine)

The specific diamine for synthesizing the polyamic acid (P) may be any of an aliphatic diamine, an alicyclic diamine, an aromatic diamine, etc., and specifically, it is preferably the following formula (3- 1a) the compound represented.

H ₂ NX ¹ -Y ¹ -X ¹ -NH ₂ (3-1a) (In the formula (3-1a), X ¹ and Y ^{1 have} the same meanings as the above formula (1))

Regarding X ¹ and Y ¹ of the formula (3-1a), the description of X ¹ and Y ¹ of the formula (1) can be applied. The specific diamine is preferably an aromatic diamine.

Specific examples of the specific diamine include a compound represented by the following formula (3-1) to formula (3-83), and the like.

[化15]

[化18]

A preferred specific example of the specific diamine is a compound in which Y ¹ in the formula (3-1a) is a group represented by the formula (Y-1), and specifically, the following formula (3- A) is indicated.

(In the formula (3-A), the meanings of R ¹ , R ² and p are the same as the formula (Y-1), and the meaning of the formula X ^{1 is} the same as the formula (2))

Regarding X ¹ of the formula (3-A), the description of X ¹ of the formula (1) can be applied. Further, with respect to R ¹ and R ^2, R respectively use the formula (Y-1) ¹ and R ² is described. p is preferably 1.

Specific examples of the compound represented by the formula (3-A) include the formula (3-1) to the formula (3-13), the formula (3-16), the formula (3-19), and the formula. (3-64), formula (3-65) And a compound represented by the formula (3-68) to the formula (3-83), and the like.

Further, the compound represented by the formula (3-A) can be synthesized by appropriately combining a common method of organic chemistry. As an example, a method of synthesizing a dinitro intermediate having a nitro group instead of the two primary amino groups in the formula (3-A), and then using an appropriate reduction system, may be mentioned. The nitro group of the base intermediate is aminated. The method of synthesizing the dinitro intermediate can be appropriately selected depending on the target compound.

The specific diamine used for the synthesis of the poly-proline may be used singly or in combination of two or more kinds.

(other diamines)

The diamine used for the synthesis of the polymer (P) may be used alone or in combination with a specific diamine.

Examples of the other diamine include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples of the diamine include aliphatic m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. And the alicyclic diamine may, for example, be 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl. Thioether, 4,4'-diaminodiphenylamine, 4-aminophenyl-4'-aminobenzoate, 1,7-bis(4-aminophenoxy)heptane, 2,2'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-di Aminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-double [ 4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene) Diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, N,N '-bis(4-aminophenyl)-benzidine, 3,5-diamine Benzoic acid, dodecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteric Alkoxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzimidyloxy)cholestane, 4 -(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 2,4-diamino-N,N-diallylaniline, 4 -aminobenzylamine, 1-(2,4-diaminophenyl)pyridazine-4-carboxylic acid, 1,3-bis(N-(4-aminophenyl)acridinyl)propane, 1-(4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine, 1-(4-aminophenyl)-2,3 -Dihydro-1,3,3-trimethyl-1H-indol-6-amine, 4-aminophenyl-4'-aminobenzoate, 4,4'-[4,4'- Propane-1,3-diylbis(acridine-1,4-diyl)]diphenylamine, and the following formula (A-1) (In the formula (A-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single Key or alkanediyl group having a carbon number of 1 to 3; a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1; wherein a and b are not simultaneously 0 )

The compound represented, etc.; For example, 1,3-bis(3-aminopropyl)-tetramethyldioxane and the like can be used, and in addition to the above, Japanese Patent Laid-Open Publication No. 2010-97188 can be used. The diamines are described.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _d -" in the formula (A-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, -O-, *-COO - or -OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). Specific examples of the radical "-C _c H _2c+1 " include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, N-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecane Base, n-icosyl group, etc. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the formula (A-1) include a compound represented by the following formula (A-1-1) to formula (A-1-4), and the like.

In addition, one type of these compounds may be used alone or two or more types may be appropriately selected and used as the other diamine for synthesizing the polyamic acid.

The preferred use ratio of the specific diamine differs depending on the synthesis method of the polyamic acid (P). For example, in the case of the method of (ii), relative to for synthesis The total amount of the diamine of the polyamic acid (P) is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20, of the specific diamine. More than Mole. The upper limit of the use ratio is not particularly limited, and may be arbitrarily set within a range of 100 mol% or less depending on various characteristics (for example, pretilt characteristics) imparted to the polymer.

When the liquid crystal alignment agent of the present invention is used for producing a twisted nematic (TN) type, a super twisted nematic (STN) type or a vertical alignment type liquid crystal display element, the liquid crystal can be used. At least a part of the polymer (P) contained in the alignment agent is a polymer having a group capable of imparting a pretilt angle expressing ability to the coating film (hereinafter also referred to as "pretilt angle expressing group"). Examples of the pretilt-expressing group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a group having a steroid skeleton having 17 to 51 carbon atoms. A group having a polycyclic structure or the like.

For example, polylysine (P) having a pretilt-expressing group can be obtained as a polymerization of the other diamine by including a diamine having a pretilt-representing group in the monomer composition. When a diamine having a pretilt-representative group is used, the amount of use thereof may be appropriately set according to the target pretilt angle, and may be, for example, 1 mol% or more based on the total diamine used for the synthesis. It is preferably set to 3 mol% to 70 mol%.

When the liquid crystal alignment ability is imparted to the coating film produced by using the liquid crystal alignment agent of the present invention by the photo-alignment method, at least one of the polymers (P) contained in the liquid crystal alignment agent may be made to have light. A polymer of an oriented structure.

Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposable photo-alignment unit. Specifically, the photo-alignment structure may be a group which exhibits photo-alignment by photoisomerization, photodimerization, photodecomposition or the like, and examples thereof include those containing azobenzene or a derivative thereof as a basic skeleton. a group having an azobenzene group, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, and a diphenyl group a ketone-containing group having a ketone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimine or a derivative thereof as a basic skeleton Polyimine-containing structure, unsaturated bond-containing structure having a carbon-carbon unsaturated bond introduced into the main chain of the polymer, and the following formula (p-1) (In the formula (p-1), X ³ is a sulfur atom, an oxygen atom or -NH-; "*" represents a bond, respectively; wherein at least one of the two "*" is bonded to the aromatic ring) The partial structure shown is introduced into an aromatic ring-CO-containing structure or the like on the main chain of the polymer.

In the formula (p-1), the aromatic ring bonded to at least one of X ³ and a carbonyl group may, for example, be a benzene ring, a naphthalene ring or an anthracene ring. Among these aromatic rings, a benzene ring is preferred from the viewpoint of liquid crystal alignment and transparency. In the two "*"s in the formula (p-1), the structure of the side not bonded to the aromatic ring is not particularly limited, and examples thereof include a chain hydrocarbon structure, an aliphatic ring, and an aromatic ring (including aroma). A hydrocarbon ring and an aromatic heterocyclic ring), an alicyclic hetero ring, and the like. Among these structures, in terms of sensitivity to light, it is preferred that two "*"s are bonded to the aromatic ring, and more preferably bonded to the aromatic hydrocarbon ring. In terms of the aspect of sensitivity to light, and in terms of broad aspect options available monomers aspect X ³ is preferably a sulfur atom, it is easy to obtain, and X ³ is preferably an oxygen atom.

In the case where the liquid crystal alignment agent of the present invention is used for photoalignment use, at least a part of the polymer (P) is preferably a polymer having a photo-alignment structure in the main chain, and more preferably having a polyimine-containing composition. Structure or polymer containing an aromatic ring-CO structure.

In the case where the polymer (P) has a polyimine-containing structure, the polymer preferably has a bicyclo[2.2.2]octene skeleton or a cyclobutane skeleton. The polymer can be, for example, at least one of cyclobutanetetracarboxylic dianhydride and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. The tetracarboxylic dianhydride is obtained by reacting with a diamine compound containing a specific diamine.

Further, in the case where the polymer (P) has a structure containing an aromatic ring-CO, the polymer is preferably represented by "-benzene ring-COO-" or "-benzene ring-OCO-" in the main chain. Part of the structure. The polymer can be obtained, for example, by polymerization of at least any one of a tetracarboxylic dianhydride having the partial structure and a diamine having the partial structure in a monomer. Specific examples of the monomer include a compound represented by the following formula (p-1-1) to formula (p-1-6), and the like.

[化25]

In the case of synthesizing a polymer having a photo-alignment structure on the main chain, from the viewpoint of photoreactivity, the use of a monomer having a photo-alignment structure with respect to the total amount of monomers for synthesizing the polymer The ratio is preferably set to 20 mol% or more, and more preferably set to 30 mol% to 80 mol%.

[Synthesis of poly(proline) (P)]

The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the polyamic acid (P) is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 equivalent to 2 equivalents. The ratio is more preferably 0.3 to 1.2 equivalents.

When the polyamic acid (P) is synthesized, a terminal modified type polymer may be synthesized by using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. By forming the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, and monoamine compounds such as aniline, cyclohexylamine, and n-butylamine. A monoisocyanate compound such as phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include an aprotic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol solvent (the organic solvent of the first group) or an organic solvent selected from the first group is preferably used. One or more kinds of a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the organic solvent of the first group and the organic solvent of the second group. Hereinafter, it is especially preferably 30% by weight or less.

It is particularly preferred to use a group selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, γ-butyrolactone. One or more of a group consisting of tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or preferably, these solvents are used within the range of the ratio. A mixture of one or more kinds with other organic solvents.

The amount (a) of the organic solvent to be used is preferably in an amount of from 0.1% by weight to 50% by weight based on the total amount (a+b) of the reaction solution, and the total amount (b) of the tetracarboxylic dianhydride and the diamine. The reaction temperature in the synthesis reaction of polylysine is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. In addition, the reaction time is preferably 0.1 hours~ 24 hours, more preferably 0.5 hours to 12 hours.

The reaction solution obtained by dissolving poly-proline (P) was obtained as described above. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline (P) contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal alignment agent, or the separated polylysine may be used. After purification, it is supplied to the preparation of the liquid crystal alignment agent. In the case where polylysine (P) is subjected to dehydration ring closure to form a polyimine, the reaction solution may be directly supplied to a dehydration ring-closure reaction, or a polylysine contained in the reaction solution may be used ( P) is separated and supplied to the dehydration ring-closure reaction, or the isolated polylysine (P) may be purified and then supplied to the dehydration ring closure reaction. The separation and purification of polylysine can be carried out according to a known method.

[Polyurethane (P)]

The polyphthalate ester (hereinafter also referred to as polyphthalate (P)) as the polymer (P) can be obtained, for example, by the following method: [I] the polyamine obtained by the synthesis reaction a method for reacting an acid (P) with a hydroxyl group-containing compound and an esterifying agent; [II] a method for reacting a tetracarboxylic acid diester with a diamine; [III] a tetracarboxylic acid diester dihalide with a diamine The method of carrying out the reaction, and the like.

Here, examples of the esterifying agent used in the method [I] include an acetal compound, a halide, and an epoxy group-containing compound. Specific examples of the compound include a hydroxyl group-containing compound such as an alcohol such as methanol, ethanol or propanol, or a phenol such as phenol or cresol. Examples of the acetal compound include N,N-dimethyl group. Hydrazine diethyl acetal, N,N-diethylformamide diethyl acetal, etc.; halides, for example, methyl bromide, bromoethane, octadecane, methyl chloride, Chloro octadecane, 1,1,1- Trifluoro-2-iodoethane or the like; examples of the epoxy group-containing compound include propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can be obtained by subjecting a tetracarboxylic dianhydride to ring opening using the alcohol. Further, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting a tetracarboxylic acid diester obtained in the above manner with a suitable chlorinating agent such as sulfinium chloride. The diamine used in the method [II] and the method [III] preferably contains the specific diamine, and the other diamine may be used as needed. Further, the polyphthalate (P) may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

[polyimine (P)]

The polyimine (hereinafter also referred to as polyimine (P)) as the polymer (P) can be dehydrated by, for example, dehydrating and ring-closing the polylysine (P) synthesized in the manner described. Obtained by imidization.

The polyimine (P) may be a fully ruthenium imide formed by dehydration ring closure of the proline structure of the polyglycolic acid (P) as a precursor thereof, or may be only ruthenium A part of the structure of the amine acid undergoes a dehydration ring closure to form a partial quinone imide of the proline structure and the quinone ring structure. The polyimide imidization ratio of the polyimine contained in the liquid crystal alignment agent of the present invention is preferably 30% or more, more preferably 40% to 99%, and particularly preferably 50% to 99%. The ruthenium imidation ratio is a total of the number of the guanidine structure of the polyimine and the number of the quinone ring structure, and the ratio of the number of the quinone ring structure is expressed as a percentage. Here, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by the following method: A method in which proline is heated; or a method in which polylysine is dissolved in an organic solvent, a dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and heating is carried out as needed. Among them, a method using the latter is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably set to 0.01 mol to 20 mol with respect to 1 mol of the proline structure of polylysine. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. The amount of the dehydration ring-closure catalyst used is preferably set to 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring closure reaction can be exemplified as an organic solvent exemplified for the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing polyimine (P) was obtained in the manner described. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent and the dehydration ring closure catalyst can be removed from the reaction solution, and then supplied to the preparation of the liquid crystal alignment agent, or the polyphthalimide can be separated and then supplied to the liquid crystal alignment. The preparation of the agent, or the separation of the separated polyimine, may be further provided to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method. In addition to this, polyimine (P) can also be obtained by ruthenium imidization of polyphthalate (P).

The polyproline (P), polyphthalate (P) and polyimine (P) obtained in the above manner are preferably such that when they are made into a solution having a concentration of 10% by weight, 10mPa. s~800mPa. The solution viscosity of s is more preferably 15 mPa. s~500mPa. s solution viscosity. Further, the solution viscosity (mPa.s) of the polymer is a concentration of 10 weights prepared for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. % polymer solution, measured using an E-type rotary viscometer at 25 ° C.

The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyphthalate, and polyimine is preferably 1,000 to 500,000. More preferably, it is 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, and more preferably 10 or less. By virtue of the molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains the polymer (P), and may contain other components as needed. Other components which can be added to the liquid crystal alignment agent include, for example, a polymer other than the polymer (P) and a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"). ), a functional decane compound, and the like.

[Other polymers]

The other polymers can be used to improve solution properties or electrical properties. The other polymer is a polymer which does not have the partial structure represented by the formula (1), and the main skeleton thereof is not particularly limited. Specifically, for example, polylysine, polyimine, and Polyphthalate, polyorganosiloxane, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmethylenebuteneimide) A polymer such as a poly(meth)acrylate or the like as a main skeleton. Among these polymers, at least one polymer selected from the group consisting of polyproline, polyphthalate, polyimine, and polyorganosiloxane is preferable.

When the other polymer is added to the liquid crystal alignment agent, the compounding ratio of the other polymer is preferably 50 parts by weight or less, based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent. It is preferably 0.1 parts by weight to 40 parts by weight, and particularly preferably 0.1 parts by weight to 30 parts by weight or less.

[epoxy group-containing compound]

The epoxy group-containing compound can be used to improve the adhesion or electrical properties of the liquid crystal alignment film to the surface of the substrate. Examples of the epoxy group-containing compound include the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl Alcohol diglycidyl ether, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl- Aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and the like. In addition to the above, examples of the epoxy group-containing compound include the epoxy group-containing polyorganosiloxane having the disclosure of WO 2009/096598.

When the epoxy compound is added to the liquid crystal alignment agent, the compounding ratio of the epoxy compound is preferably 40 parts by weight or less based on 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. More preferably, it is 0.1 weight part - 30 weight part.

[functional decane compound]

The functional decane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyl group. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethoxy矽alkylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazepineacetic acid Ester, methyl 9-trimethoxydecyl-3,6-diazadecanoate, N-benzyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethyl Oxaloxane, glycidoxymethyltrimethoxydecane, 2-glycidoxyethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and the like.

In the case where the functional decane compound is added to the liquid crystal alignment agent, the compounding ratio of the functional decane compound is preferably 2 parts by weight based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent. Hereinafter, it is more preferably 0.02 parts by weight to 0.2 parts by weight.

Further, an additive generally used for preparing a liquid crystal alignment agent can be used as its His ingredients. Examples of the other additives include a compound having at least one oxetanyl group in the molecule, an antioxidant, a surfactant, and the like.

<solvent>

The liquid crystal alignment agent of the present invention is prepared by dispersing or dissolving the polymer (P) and other components as needed, preferably in a suitable solvent.

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethyl Ethylamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionic acid Ester, 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, B Glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethyl Glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, and the like. These organic solvents may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, and the like. It is in the range of 1% by weight to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate by a method described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. At this time, the solid content concentration is less than 1% by weight. In the case of the film thickness of the coating film, it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, and the coating property is lowered. tendency.

The range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of the rotator method, the solid content concentration (the ratio of the total weight of all the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is particularly preferably 1.5% by weight to 4.5% by weight. The scope. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% by weight to 9% by weight, thereby setting the solution viscosity to 12 mPa. s~50mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by weight to 5% by weight, thereby setting the solution viscosity to 3 mPa. s~15mPa. The scope of s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C, and more preferably from 20 ° C to 30 ° C.

[Liquid crystal alignment film and liquid crystal display element]

The liquid crystal alignment film can be produced by the liquid crystal alignment agent of the present invention described above. The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display device of the present invention is not particularly limited, and can be applied to, for example, a TN type, an STN type, or a vertical alignment (VA) type (including Vertical Alignment-Multidomain Vertical Alignment (Vertical Alignment-Multidomain Vertical Alignment, VA-MVA), Vertical Alignment-Patterned Vertical Alignment (VA-PVA), etc. Switching (In-Plane Switching, IPS) type, Fringe Field Switching (FFS) type, Optically Compensatory Bend (OCB) type and other modes of operation.

The liquid crystal display element of the present invention can be produced, for example, by the steps including the following steps (1-1) to (1-3). Step (1-1) uses different substrates depending on the desired mode of operation. Step (1-2) and step (1-3) are shared in each operation mode.

[Step (1-1): Formation of Coating Film]

First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate.

(1-1A) In the case of manufacturing a liquid crystal display element such as a TN type, an STN type or a VA type, first, two substrates provided with a patterned transparent conductive film are used as a pair, and the respective transparency is used. On the conductive film forming surface, the liquid crystal alignment agent of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method, respectively. For the substrate, for example, glass such as float glass or soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and poly(alicyclic olefin) may be used. Transparent substrate. The transparent conductive film provided on one side of the substrate may be a Neisser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Indium Tin Oxide (ITO) film or the like. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and a mask having a desired pattern when forming a transparent conductive film may be used. ) method, etc. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is formed may be coated with a functional decane compound or a functional titanium compound. Pre-processing.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing the sag of the applied liquid crystal alignment agent. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Then, the firing (post-baking) step is carried out for the purpose of completely removing the solvent and thermally amidating the proline structure present in the polymer as needed. The firing temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed in the above manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-1B) In the case of manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode (including a transparent conductive film or a metal film patterned into a comb-tooth type) and The liquid crystal alignment agent of the present invention is applied to one surface of the counter substrate on which the electrodes are provided, and then each coated surface is heated to form a coating film. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film , the same as the above (1-1A). As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the cases (1-1A) and (1-1B), After the liquid crystal alignment agent is applied onto the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film of the liquid crystal alignment film. In this case, by further heating after the formation of the coating film, the polyglycolic acid, the polyamidomate, and the polyimine which are formulated in the liquid crystal alignment agent of the present invention may be subjected to a dehydration ring closure reaction. Further yttrium imidized coating film.

[Step (1-2): Orientation ability treatment]

In the case of manufacturing a liquid crystal display element of a TN type, an STN type, an IPS type or an FFS type, a process of imparting a liquid crystal alignment ability to the coating film formed in the above step (1-1) is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. The alignment ability imparting treatment may be exemplified by a rubbing treatment in which a coating film is wound with a cloth including fibers such as nylon, rayon, or cotton, and the coating film is wiped in a predetermined direction; and a light alignment treatment is performed to irradiate the coating film with polarized light. Or non-polarized radiation. On the other hand, in the case of producing a VA liquid crystal display element, the coating film formed in the above step (1-1) can be directly used as a liquid crystal alignment film, and the alignment ability imparting treatment can be performed on the coating film.

When the liquid crystal alignment ability is imparted to the coating film by the photo-alignment treatment, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used as the radiation to be applied to the coating film. In the case where the radiation is polarized, it may be linearly polarized or partially polarized. Further, when the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction, or these irradiations may be combined. When the non-polarized radiation is irradiated, the direction of the irradiation is an oblique direction.

As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in a preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, or the like. The radiation exposure is preferably ^{100J / m 2 ~ 50,000J / m} 2, and more preferably ^{300J / m 2 ~ 20,000J / m} 2. Further, in order to improve the reactivity, the coating film may be irradiated with light while heating the coating film. The temperature at the time of heating is usually from 30 ° C to 250 ° C, preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C.

Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment so that the liquid crystal alignment film has different liquid crystal alignment ability in each region: a part of the liquid crystal alignment film is irradiated by irradiating a part of the liquid crystal alignment film with ultraviolet rays. The treatment of changing the pretilt angle or the process of removing the resist film after performing a rubbing treatment in a direction different from the previous rubbing treatment after forming a resist film on a part of the surface of the liquid crystal alignment film. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a polymer sustained alignment (PSA) type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell]

Two substrates in which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a previously known method. First, the two substrates are opposed to each other via a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant. After filling the liquid crystal into the cell gap divided by the sealant, the injection hole is sealed, thereby manufacturing a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. a predetermined portion on one of the two substrates on which the liquid crystal alignment film is formed, for example, an ultraviolet curable sealant, and further, after a liquid crystal is dropped on a predetermined portion of the liquid crystal alignment film surface, The liquid crystal alignment film is bonded to the other substrate in a facing manner, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealing agent, thereby manufacturing a liquid crystal cell. In the case of using any of the methods, it is preferred to remove the liquid crystal cell produced as described above and further to the temperature of the isotropic phase after heating to the liquid crystal used, and then gradually cool to room temperature, thereby removing Flow alignment when liquid crystal is filled.

As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used.

The liquid crystal may, for example, be a nematic liquid crystal or a smectic liquid crystal, and among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal or an azoxy may be used. Liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane A liquid crystal, a cubane liquid crystal, or the like. In addition, it is also possible to use the following substances in these liquid crystals: for example, cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate, etc. (cholesteric liquid crystal) ); as the trade name "C-15", "CB-15" (Merck (Merck) Produced by chiral agent; iron such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate Ferroelectric liquid crystal, etc.

Next, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film or a polarizing plate including the H film itself. The H film "a film obtained by absorbing iodine while extending the polyvinyl alcohol.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for: watches, portable game machines, word processors, notebook personal computers, car navigation systems, video cameras, personal digital assistants (Personal Digital Assistant) , PDA), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices.

[Examples]

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

In the following examples, the solution viscosity of the polymer solution was measured by the following method. Further, in the following, the compound represented by the formula X may be simply referred to as "compound X".

[Solid viscosity of polymer solution]

Solution viscosity of polymer solution [mPa. s] is prepared by using a predetermined solvent A solution having a polymer concentration of 10% by weight was measured at 25 ° C using an E-type rotational viscometer.

<Synthesis of Compounds>

[Example 1-1: Synthesis of Compound (DA-1)]

The compound represented by the following formula (DA-1) was synthesized according to the following Scheme 1.

2.5 g of 2-chloro-5-nitropyridine was suspended in 25 ml of toluene, and 1.88 g of triethylamine was added thereto. A solution obtained by dissolving 0.5 g of pyridazine in 2 ml of chloroform was gradually added dropwise to the container. After stirring at room temperature for 30 minutes, it was stirred at 80 ° C for 12 hours. At this time, as the reaction progressed, a yellow solid precipitated. After cooling, the solid was filtered, washed thoroughly with water, and then ethyl acetate was used to remove toluene. The obtained solid was dried to obtain 1.94 g of a compound (DA-1-1) having a purity of 99%.

Then, a three-necked flask in which 0.3 g of Pd/C was taken was subjected to nitrogen substitution, and 40 ml of oxygen-deaerated ethanol was added thereto, followed by stirring. 1.94 g of the compound (DA-1-1) was added to the vessel, cooled to 0 ° C, and stirred for 5 minutes. After stirring, 5 ml of hydrazine monohydrate was gradually added dropwise to the reaction solution.

The mixture was stirred at 0 ° C for 3 hours and at room temperature for 6 hours to complete the reaction. add 100 ml of ethyl acetate and 80 ml of THF were added, followed by the addition of 60 ml of pure water, which was separated. After liquid separation was carried out again in pure water, it was concentrated, and 1.5 g of a compound (DA-1) having a purity of 99% was obtained as a yellow-white solid.

[Example 1-2: Synthesis of Compound (DA-2)]

The compound represented by the following formula (DA-2) was synthesized according to the following Scheme 2.

2.68 g of 2-chloro-5-nitropyridine was suspended in 25 ml of toluene, and 1.99 g of triethylamine was added thereto. A solution obtained by dissolving 0.51 g of N,N'-dimethylethylenediamine in 2 ml of chloroform was gradually added dropwise to the container. After stirring at room temperature for 30 minutes, it was stirred at 80 ° C for 12 hours. At this time, as the reaction progressed, a yellow solid precipitated. After cooling, the solid was filtered, washed thoroughly with water, and then ethyl acetate was used to remove toluene. The solid was dried to obtain 1.69 g of a compound (DA-2-1) having a purity of 96%.

Then, a three-necked flask in which 0.3 g of Pd/C was taken was subjected to nitrogen substitution, and 40 ml of oxygen-deaerated ethanol was added thereto, followed by stirring. 1.69 g of the compound (DA-2-1) was added to the vessel, cooled to 0 ° C, and stirred for 5 minutes. After stirring, 5 ml of hydrazine monohydrate was gradually added dropwise to the reaction solution.

The mixture was stirred at 0 ° C for 3 hours and at room temperature for 6 hours to complete the reaction. 100 ml of ethyl acetate and 80 ml of THF were added, followed by the addition of 60 ml of pure water, which was separated. After liquid separation was carried out again in pure water, it was concentrated to give a compound (DA-2), 1.18 g, as a yellow solid as a yellow solid.

[Example 1-3: Synthesis of Compound (DA-3)]

The compound represented by the following formula (DA-3) was synthesized according to the following Scheme 3.

2.82 g of 2-chloro-5-nitropyrimidine was suspended in 25 ml of toluene, and 1.99 g of triethylamine was added thereto. A solution obtained by dissolving 0.5 g of pyridazine in 2 ml of chloroform was gradually added dropwise to the container. After stirring at room temperature for 30 minutes, it was stirred at 80 ° C for 12 hours. At this time, as the reaction progressed, a yellow solid precipitated. After cooling, the solid was filtered, washed thoroughly with water, and then ethyl acetate was used to remove toluene. The solid was dried to obtain 1.51 g of a compound (DA-3-1) having a purity of 98%.

Then, a three-necked flask in which 0.3 g of Pd/C was taken was subjected to nitrogen substitution, and 40 ml of oxygen-deaerated ethanol was added thereto, followed by stirring. 1.51 g of the compound (DA-3-1) was added to the vessel, cooled to 0 ° C, and stirred for 5 minutes. After stirring, 5 ml of hydrazine monohydrate was gradually added dropwise to the reaction solution.

The mixture was stirred at 0 ° C for 3 hours and at room temperature for 6 hours to complete the reaction. add 100 ml of ethyl acetate and 80 ml of THF were added, followed by the addition of 60 ml of pure water, which was separated. After liquid separation was carried out again in pure water, it was concentrated to give a compound (DA-3), 1.02 g, as a yellow solid as a yellow solid.

[Example 1-4: Synthesis of Compound (DA-4)]

The compound represented by the following formula (DA-4) was synthesized according to the following Scheme 4.

2.5 g of 4-chloro-2-nitropyridine was suspended in 25 ml of toluene, and 1.88 g of triethylamine was added thereto. A solution obtained by dissolving 0.5 g of pyridazine in 2 ml of chloroform was gradually added dropwise to the container. After stirring at room temperature for 30 minutes, it was stirred at 80 ° C for 12 hours. At this time, as the reaction progressed, a yellow solid precipitated. After cooling, the solid was filtered, washed thoroughly with water, and then ethyl acetate was used to remove toluene. The solid was dried to obtain 1.78 g of a compound (DA-4-1) having a purity of 96%.

Then, a three-necked flask in which 0.3 g of Pd/C was taken was subjected to nitrogen substitution, and 40 ml of oxygen-deaerated ethanol was added thereto, followed by stirring. 1.78 g of the compound (DA-4-1) was added to the vessel, cooled to 0 ° C, and stirred for 5 minutes. After stirring, 5 ml of hydrazine monohydrate was gradually added dropwise to the reaction solution.

The mixture was stirred at 0 ° C for 3 hours and at room temperature for 6 hours to complete the reaction. Add 100 ml of ethyl acetate and 80 ml of THF, and then add 60 ml of pure water to carry out Liquid separation. After liquid separation was carried out again in pure water, it was concentrated to give a compound (DA-4), 1.44 g, as a yellow-white solid.

[Example 1-5: Synthesis of Compound (DC-1)]

The compound represented by the following formula (DC-1) was synthesized according to the following Scheme 5.

2.7 g of the compound (DA-1) was suspended in 25 ml of pure water, and 5.6 g of potassium hydroxide and 13.9 g of bromoacetic acid were added thereto, followed by stirring at 90 ° C for 12 hours. At this time, as the reaction proceeds, it changes to brown. After cooling, the reaction liquid was poured into 100 mL of cold concentrated hydrochloric acid, and the solid obtained by reprecipitation was filtered, and washed thoroughly with water. The solid was dried to obtain 3.6 g of a compound (DC-1-1) having a purity of 98%.

Then, 3.6 g of the compound (DC-1-1) and 20 mL of acetic anhydride were placed in a container, and the mixture was stirred at 60 ° C for 6 hours. The solid which precipitated after cooling was filtered, and 2.2 g of a compound (DC-1) having a purity of 98% was obtained as a yellow-white solid.

<Synthesis of Polymer>

[Example 2-1: Synthesis of polyproline (P1)]

50 moles of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 50 mole parts of pyromellitic dianhydride as tetracarboxylic dianhydride, 50 moles of p-phenylenediamine as diamine And 50 parts of the compound (DA-1), dissolved in N-methyl-2-pyrrolidone (NMP), and reacted at 60 ° C for 6 hours to obtain a polyglycine containing 20% by weight. Solution. The obtained polyaminic acid solution was divided into small amounts, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the obtained solution viscosity was 80 mPa. s.

[Example 2-2 to Example 2-28 and Synthesis Example 2-29 to Synthesis Example 2-32]

The polyperglycine (P2)-poly was synthesized in the same manner as in the above Example 2-1 except that the type and amount of the tetracarboxylic dianhydride and the diamine used were changed as described in Table 1 below. Proline (P32).

In Table 1, the numerical values in the parentheses of the tetracarboxylic dianhydride and the diamine indicate the use ratio [mol%] with respect to the total of 100 moles of the tetracarboxylic dianhydride used for the synthesis of the polymer. The abbreviations in Table 1 have the following meanings.

<tetracarboxylic dianhydride>

T-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

T-2: pyromellitic dianhydride

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

T-4: p-phenylene bis(trimellitic acid monoester anhydride)

T-5: 1R, 2S, 4S, 5R-1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride

T-6: ethylenediaminetetraacetic acid dianhydride

<Diamine>

D-1: p-phenylenediamine

D-2: 4,4'-diaminodiphenyl ether

D-3: 3,5-diaminobenzoic acid

D-4: 4-aminophenyl-4'-aminobenzoate

D-5: a compound represented by the following formula (d-5)

D-6: a compound represented by the following formula (d-6)

D-7: a compound represented by the following formula (d-7)

DA-5: a compound represented by the following formula (DA-5)

DA-6: a compound represented by the following formula (DA-6)

[Example 1A]

(1) Preparation of liquid crystal alignment agent

In the polyphthalic acid (P1) obtained in the above Example 2-1 as a polymer, NMP and butyl cellosolve (BC) were added as a solvent to prepare a solvent composition of NMP:BC=50: 50 (weight ratio), a solution having a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (S1).

(2) Manufacturing of liquid crystal display element for friction alignment

The prepared liquid crystal alignment agent (S1) was applied by a spinner on a glass substrate having a thickness of 1 mm on one side of a chrome electrode provided in a comb shape. Then, after prebaking on a hot plate at 80 ° C for 1 minute, it was baked on a hot plate at 230 ° C for 10 minutes to form a coating film having a film thickness of about 800 Å. A rubbing machine having a roll of a nylon cloth wound was used for the formed coating film surface, and rubbing treatment was performed at a rotation speed of the roll of 1,000 rpm, a moving speed of the stage of 25 mm/sec, and a hair pressing length of 0.4 mm to impart a liquid crystal. Orientation capability. Further, the substrate was ultrasonically washed in ultrapure water for 1 minute, and dried in a 100 ° C clean oven for 10 minutes to produce a substrate having a liquid crystal alignment film on a surface having a comb-shaped chrome electrode. The substrate having the liquid crystal alignment film was referred to as "substrate A".

In addition, a coating film of the liquid crystal alignment agent (S1) was formed on the surface of the glass substrate having a thickness of 1 mm without the electrode, and rubbing treatment was carried out, followed by washing and drying to produce liquid crystal on one side. The substrate of the alignment film. The substrate having the liquid crystal alignment film was referred to as "substrate B".

Then, on the outer edge of the surface of the substrate A having the liquid crystal alignment film, coating is applied After the epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is inserted, the rubbing directions in the respective liquid crystal alignment films are antiparallel, and the two substrates A and B are opposed to each other via the gap. The edges are abutted against each other and crimped to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-2042) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to manufacture an IPS type. Liquid crystal cell.

(3) Evaluation of reliability

The reliability was evaluated using the liquid crystal cell manufactured in the above (2). Evaluation was performed in the following manner. First, with respect to the liquid crystal cell, a voltage of 5 V was applied with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio (VHR1) after 167 milliseconds from the application release was measured. Then, the liquid crystal cell was allowed to stand in an 80 ° C oven irradiated with a light-emitting diode (LED) lamp for 200 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. After cooling, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio (VHR2) after 167 milliseconds from the application release was measured. Further, the measuring device was "VHR-1" manufactured using Toyo Technica Co., Ltd. The rate of change (ΔVHR) of the VHR at this time was calculated by the following formula (2), and the reliability was evaluated based on ΔVHR. In the evaluation, the case where ΔVHR is less than 1% is determined as the reliability “good (◎)”, and the case where 1% or more and less than 2% is determined as the reliability “may (○)”, and the case of 2% or more is determined. For reliability "bad (x)". As a result, the reliability was "good" in Example 1A.

△VHR[%]=(VHR1-VHR2)/(VHR1)×100...(2)

(4) Evaluation of liquid crystal alignment

In the liquid crystal cell produced in the above (2), the presence or absence of an abnormal region when the voltage is turned on (applied or released) is observed by a polarizing microscope, and the case where there is no abnormal region is determined as "good" liquid crystal alignment, and In the case where there is one abnormal region, it is determined that the liquid crystal alignment is "defective". As a result, the liquid crystal alignment property of the liquid crystal cell of this example was "good".

(5) Afterimage characteristics (image residual characteristics)

In addition to the substrate, a glass substrate having two metal crystal electrodes (electrode a and electrode b) patterned in a comb-like shape including chromium and a counter-glass substrate not provided with an electrode are used as a pair. An IPS type liquid crystal cell was fabricated in the same manner as in the above (2). Then, a polarizing plate was bonded to both outer surfaces of the substrate of the liquid crystal cell to manufacture a liquid crystal display element. The IPS liquid crystal display element was placed in an environment of 25 ° C and 1 atmosphere, and no voltage was applied to the electrode b, and a combined voltage of an alternating current voltage of 3.5 V and a direct current voltage of 5 V was applied to the electrode a for 2 hours. Then, an alternating current of 4 V was applied to both the electrode a and the electrode b. The time from when the voltage of the alternating current of 4 V was applied to the two electrodes was reached until the difference in light transmittance between the electrodes a and b was not confirmed by visual observation. The afterimage characteristics when the time is less than 100 seconds are evaluated as "good", and the afterimage characteristics when 100 seconds or more and less than 150 seconds are evaluated as "OK", and the afterimage characteristics in the case of more than 150 seconds are evaluated. It is "bad". As a result, in the liquid crystal cell of Example 1A, the afterimage characteristics were good. good result.

[Example 2A to Example 11A, Example 28A, and Comparative Example 1 and Comparative Example 2]

A liquid crystal alignment agent (S2) to a liquid crystal alignment agent (S11) were prepared by the same solvent ratio and solid content concentration as those of the above-mentioned Example 1A, except that the type of the polymer to be used was changed as shown in the following Table 2. And liquid crystal alignment agent (S28) ~ liquid crystal alignment agent (S30). Further, a liquid crystal cell was produced in the same manner as in Example 1A using each liquid crystal alignment agent, and various evaluations were performed using the obtained liquid crystal cell. The results are shown in Table 2 below.

[Example 12A]

(1) Preparation of liquid crystal alignment agent

A liquid crystal alignment agent (S12) was prepared in the same solvent ratio and solid content concentration as in Example 1A except that the type of the polymer to be used was changed to polyamine acid (P12).

(2) Manufacturing of liquid crystal display element for optical alignment film

The prepared liquid crystal alignment agent (S12) was applied by a spinner to a glass substrate having a thickness of 1 mm on one side of a chrome electrode provided in a comb shape, and the film thickness was set to 0.1 μm at 80 ° C. After prebaking for 1 minute on a hot plate, post-baking was performed on a hot plate at 230 ° C for 10 minutes to form a coating film. The substrate having the coating film was referred to as "substrate A".

In addition, a coating film of the liquid crystal alignment agent (S12) was formed in the same manner as described above on the side of the glass substrate having the electrode thickness of 1 mm. Will have the coating The substrate of the film serves as "substrate B".

Then, the surface of the coating film of the substrate A and the substrate B was irradiated with a polarized ultraviolet ray of 10,000 J/m ² containing an open line of 254 nm from the normal direction of the substrate using an Hg-Xe lamp to form a liquid crystal alignment film.

Next, with respect to the pair of substrates subjected to the light irradiation treatment, a liquid crystal injection port was left at the edge of the surface on which the liquid crystal alignment film was formed, and an alumina ball having a diameter of 5.5 μm was applied by screen printing. After the epoxy resin adhesive, the projection direction of the polarizing axis on the substrate surface when the light was irradiated was antiparallel, and the substrate was pressure-bonded and laminated, and the adhesive was thermally cured at 150 ° C for 1 hour. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-7028) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it was heated at 150 ° C and then slowly cooled to room temperature. Then, a polarizing plate was bonded to both sides of the substrate to fabricate a liquid crystal display element.

(3) Evaluation of reliability

The reliability was evaluated in the same manner as in the above-described Embodiment 1A except that the liquid crystal display element manufactured in the above (2) was used. As a result, ΔVHR=1.6% in this embodiment, which is "OK" for reliability. result.

(4) Evaluation of liquid crystal alignment

The reliability was evaluated in the same manner as in the above-described Example 1A except that the liquid crystal display element manufactured in the above (2) was used. As a result, liquid crystal was used in this example. Orientation "good" results.

(5) Afterimage characteristics (image residual characteristics)

The afterimage characteristics were evaluated in the same manner as in the above-described Example 1A except for the use of the liquid crystal alignment agent (S12). As a result, in this example, the afterimage characteristics were evaluated.

[Example 13A to Example 27A, Comparative Example 3, and Example 4]

The liquid crystal alignment agent (S13) to the liquid crystal alignment agent (S27) were prepared by the same solvent ratio and solid content concentration as those of the above-mentioned Example 1A except that the type of the polymer to be used was changed as shown in the following Table 2. A liquid crystal alignment agent (S31) and a liquid crystal alignment agent (S32). Further, a liquid crystal cell was produced in the same manner as in Example 12A using each liquid crystal alignment agent, and various evaluations were performed using the obtained liquid crystal cell. The results are shown in Table 2 below.

As shown in Table 2, in each of Examples 1A to 28A, even after exposure to a light stress and a thermal stress environment for a long period of time (200 hours), the decrease in the voltage holding ratio was small, and the reliability was good. On the other hand, in Comparative Example 1 to Comparative Example 4, the voltage holding ratio was greatly lowered due to the application of optical stress and thermal stress, and the reliability was evaluated as "bad".

Further, regarding the liquid crystal alignment, no alignment failure was observed in each of Examples 1A to 28A, and any of the samples in the examples was evaluated as "good" or "may" with respect to the afterimage characteristics.

As described above, it was confirmed that the liquid crystal alignment film having the structure used in the examples does not disturb the liquid crystal alignment and has high reliability.

Claims (6)

A liquid crystal alignment agent containing a polymer (P) obtained by polymerization of a compound represented by the following formula (3) in a monomer composition, In the formula (3), X ¹ is a divalent organic group, wherein at least one of the two X ¹ is a divalent aromatic heterocyclic group containing a nitrogen atom in the ring moiety; and Z ¹ is a primary amino group or a formula ( Z-1) the base represented; In the formula (z-1), "*" represents a bond to X ¹ ; R ¹ is a single bond, an alkanediyl group having a carbon number of 1 to 6 or a cyclohexyl group, and R ² is a hydrogen atom or a carbon number of 1 to 2; The alkyl group of 6 or 2 R ^{2 is} bonded to each other to form a divalent alicyclic heterocyclic group having 2 to 10 carbon atoms together with 2 nitrogen atoms and R ¹ ; the two X ^{1 's} may be the same or different, 2 The R ² may be the same or different; p is 0 or 1, and the polymer (P) is at least one selected from the group consisting of polyproline, polyphthalate, and polyimine. The liquid crystal alignment agent according to claim 1, wherein the two X ¹ in the formula (3) are a divalent aromatic heterocyclic group containing a nitrogen atom in the ring portion. A method for producing a liquid crystal alignment film, comprising: a step of forming a coating film using a liquid crystal alignment agent according to claim 1 or 2; and applying light irradiation to the coating film to impart alignment ability to liquid crystal A step of. A method for producing a liquid crystal alignment film, comprising: a step of forming a coating film using a liquid crystal alignment agent according to claim 1 or 2; and subjecting the coating film to rubbing treatment to impart liquid crystal alignment ability A step of. A liquid crystal alignment film formed by using a liquid crystal alignment agent as described in claim 1 or 2. A liquid crystal display element comprising the liquid crystal alignment film according to item 5 of the patent application.