TW201441282A - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, phase difference film, manufacturing method of phase difference film, polymer and compound - Google Patents

Abstract

A liquid crystal aligning agent for obtaining a liquid crystal aligning film that is capable of improving various characteristics required by a liquid crystal display element is provided. The liquid crystal aligning agent contains a polymer obtained by using a compound (A) and an amine compound (B) as monomers, wherein the compound (A) is a polycarboxylic acid, a polycarboxylic acid anhydride or the like, and the amine compound (B) contains a compound represented by the following formula (1). Z1-R1-Z2 (1) (In the formula, R1 is a divalent organic group; Z1 is a nitrogen-containing heterocyclic group having 5 to 7 ring members which has a ''-NH-'' between carbon-carbon bond lying in a ring skeleton of an aliphatic ring; Z2 is a primary amino group, a nitrogen-containing heterocyclic group having 5 to 7 ring members which has a ''-NH-'' between carbon-carbon bond lying in a ring skeleton of an aliphatic ring or the like).

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, method for producing retardation film, polymer and compound

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a method for producing a retardation film and a retardation film, and a polymer which can be suitably used as a component of a liquid crystal alignment agent, and a compound for producing the polymer. .

Previously, liquid crystal display elements have developed various driving methods in which the electrode structure, the physical properties of the liquid crystal molecules used, the manufacturing steps, and the like are different, for example, a twisted nematic (TN) type or a super twisted nematic (Super Twisted Nematic) is known. Various liquid crystal display elements such as STN) type, Vertical Alignment (VA) type, In-Plane Switching (IPS) type, and Fringe Field Switching (FFS) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. In terms of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal, the material of the liquid crystal alignment film is usually polyacrylic acid or polyimide.

In order to improve the display quality of liquid crystal display elements, various liquids have been proposed previously. A crystal alignment agent (for example, refer to Patent Document 1 and Patent Document 2). Patent Document 1 discloses that a soluble polyimine obtained by a reaction of a diamine compound having two primary amine groups and a nitrogen-containing ring in a molecule with a tetracarboxylic dianhydride is used as a liquid crystal alignment agent. The polymer component is not only excellent in liquid crystal alignment, but also shortens the time until the afterimage is eliminated. Further, Patent Document 2 discloses that a liquid polysiloxane obtained by a reaction of a diamine compound having two primary amine groups and a piperazine ring in a molecule with a tetracarboxylic dianhydride is used to cause liquid crystal The heat resistance and charge leakage property of the alignment film are good.

Further, a plurality of optical materials are used for the liquid crystal display element, and the retardation film is used for the purpose of eliminating the coloration of the display or for eliminating the dependence of the display color and the contrast ratio on the viewing angle depending on the visual direction. The retardation film is known to have a liquid crystal alignment film formed on a surface of a substrate such as a triacetyl cellulose (TAC) film, and a liquid crystal formed on the surface of the liquid crystal alignment film by curing a polymerizable liquid crystal. The retardation film of the layer. Further, in recent years, when a liquid crystal alignment film in a retardation film is produced, a photo-alignment method in which a liquid crystal alignment ability is imparted by irradiating a radiation-sensitive or non-polarized radiation to a radiation-sensitive organic thin film formed on a surface of a substrate has been proposed. A liquid crystal alignment agent for a retardation film in which a liquid crystal alignment film is produced by the above method (see, for example, Patent Document 3).

A method of producing a retardation film on an industrial scale proposes a roll-to-roll method (for example, refer to Patent Document 4). The method is a method in which the film is subjected to the following steps in a continuous step, and the film after the steps is formed into a wound body, and the treatment is carried out by winding up the wound body of the elongated substrate film. A film, a process of forming a liquid crystal alignment film on the rolled film, a process of applying a polymerizable liquid crystal on the liquid crystal alignment film and curing it, and a process of laminating a protective film as needed.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-104633

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

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-37868

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-86786

In recent years, liquid crystal display elements have been used not only for display terminals such as personal computers but also for various applications such as liquid crystal televisions or car navigation systems, mobile phones, smart phones, and information displays. In addition, the demand for higher performance of the liquid crystal display element is further improved, and various characteristics required for the liquid crystal display element can be further improved as the liquid crystal alignment film.

Further, the retardation film can be easily produced on an industrial scale by using the above-described roll-to-roll method, but on the other hand, when the adhesion between the liquid crystal alignment film and the base film is insufficient, When the film is formed into a wound body after the completion of the step, the liquid crystal alignment film may be peeled off from the substrate film. In this case, there is a problem that the yield of the product is lowered.

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent for obtaining a liquid crystal alignment film which can satisfy various characteristics required for a liquid crystal display device. In addition, another object of the present invention is to provide a liquid crystal alignment agent which can form a liquid crystal alignment film for a retardation film which is excellent in liquid crystal alignment and has good adhesion to a substrate.

The inventors of the present invention have carried out the problems of the prior art as described above. As a result of the active research, it has been found that a coating film formed by using a polymer having a specific structure and a polymer obtained by polycondensation of a polyvalent carboxylic acid or a derivative thereof is excellent in light transmittance, and can be suitably used for a liquid crystal alignment film or the like. Use to solve the present invention. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, a method for producing the same, a polymer, and a compound.

An aspect of the present invention provides a liquid crystal alignment agent comprising a polymer obtained by using a compound as a monomer: a polyester carboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid halide, a partial esterified product of a polycarboxylic acid, and At least one compound (A) of the group consisting of the oxime halide of the partial esterified product; and an amine compound (B) containing a compound represented by the following formula (1).

Z ¹ -R ¹ -Z ² (1)

(In the formula (1), R ¹ is a divalent organic group; and Z ¹ is a nitrogen-containing heterocyclic ring having a ring number of 5 to 7 having a "-NH-" between carbon-carbon bonds in the ring skeleton of the aliphatic ring. a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted; Z ² is a first-order amine group, -NHR ² (R ² is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and has a R ² group; In the case of an aromatic ring, the aromatic ring is not directly bonded to a nitrogen atom, or a nitrogen-containing heterocyclic ring having a ring number of 5 to 7 between "carbon-carbon bonds" in the ring skeleton of the aliphatic ring. a ring group, the hydrogen atom bonded to the carbon atom of the nitrogen-containing heterocyclic group may be substituted; wherein, in the case where Z ² is "-NHR ² ", Z ² does not directly bond with the aromatic ring of R ¹ Knot.)

Another aspect of the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent. Further, a liquid crystal display element including the liquid crystal alignment film and a retardation film including the liquid crystal alignment film are provided. Further, on the other hand, A method for producing a retardation film, comprising: a step of applying the liquid crystal alignment agent onto a substrate to form a coating film; a step of irradiating the coating film with light; and coating the light after the irradiation A step of applying a polymerizable liquid crystal on the film to harden it. Further, at least one compound selected from the group consisting of a polyvalent carboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid halide, a partial esterified product of a polyvalent carboxylic acid, and a hydrazine halide of the partial ester compound is provided, and The polymer obtained by using the amine compound of the compound represented by the formula (1) as a monomer, and the compound represented by the formula (1).

By using the polymer obtained by using the compound represented by the above formula (1) as a polymer component of a liquid crystal alignment agent, it is possible to form a liquid crystal alignment having various properties such as coatability, light transmittance, and liquid crystal alignment property to a substrate. membrane. In addition, by forming the liquid crystal alignment film by using the liquid crystal alignment agent of the present invention, it is possible to obtain a liquid crystal display element which is excellent in heat resistance and voltage holding characteristics, and which has a rapid relaxation of the accumulated electric charge of the DC voltage, and which is less likely to cause a decrease in contrast or burn. Further, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention has good adhesion to the substrate. Therefore, when the liquid crystal alignment film and the substrate are hardly peeled off, the liquid crystal alignment film and the substrate are hardly peeled off. Therefore, for example, when the retardation film is produced, the deterioration of the product yield can be suppressed.

10‧‧‧Liquid display components

11a, 11b‧‧‧ glass substrate

12‧‧‧ bottom electrode

13‧‧‧ nitride film

14‧‧‧Upper electrode

15a, 15b‧‧‧Liquid alignment film

D1‧‧‧ line width

D2‧‧‧ distance

C1‧‧‧Parts surrounded by dotted lines

Fig. 1 is a schematic configuration diagram of an FFS type liquid crystal cell.

2 is a schematic plan view of the upper electrode. Fig. 2(a) is a plan view of the upper electrode, and Fig. 2(b) is a partially enlarged view of the upper electrode.

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 composition>

The liquid crystal alignment agent of the present invention contains a polymer (hereinafter also referred to as "polymer (P)") as a polymer component, and the polymer (P) is selected from a polycarboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid. At least one compound (A) of a group consisting of an acid halide, a partial esterified product of a polycarboxylic acid, and a hydrazine halide of the partial ester compound, and an amine compound (B) containing the compound represented by the formula (1) Obtained by carrying out the reaction.

[Compound (A)]

The polyvalent carboxylic acid as the compound (A) is a compound having two or more carboxyl groups, and the polyvalent carboxylic anhydride is an anhydride of a polyvalent carboxylic acid. Further, the compound (A) may be a partial esterified product or a hydrazine halide of the polyvalent carboxylic acid, or may be a halide of the partially esterified product.

Specific examples of the compound (A) include polyalicarboxylic acids such as malonic acid, adipic acid, succinic acid, maleic acid, and butane tetracarboxylic acid; and hexahydroorthophenylene; Dicarboxylic acid, hexahydroterephthalic acid, cyclobutane tetracarboxylic acid, cyclohexanetetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, bicyclo[3.3.0]octane-2,4, Alicyclic carboxylic acid such as 6,8-tetracarboxylic acid; phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid An aromatic polycarboxylic acid or the like.

The polyvalent carboxylic acid anhydride may, for example, be an intramolecular acid anhydride or an intermolecular acid anhydride of the above polyvalent carboxylic acid, and specific examples thereof include tetracarboxylic dianhydride and dicarboxylic anhydride.

Examples of the polyvalent carboxylic acid halide include hydrazine chloride, hydrazine bromine, and the like of the polyvalent carboxylic acid, and specific examples thereof include dicarboxylic acid dicarboxylic acid. Dichloride), dicarboxylic acid dibromide, tetracarboxylic acid dichloride, tetracarboxylic acid dibromide, and the like.

The esterified product obtained by reacting the polyvalent carboxylic acid with an alcohol or a phenol or the like is exemplified as the partial ester compound of the polyvalent carboxylic acid, and examples thereof include a tetracarboxylic acid diester. In addition, examples of the oxime halide of the partial ester compound include ruthenium chloride and ruthenium bromine of the partial ester compound, and specific examples thereof include a tetracarboxylic acid diester dichloride and a tetracarboxylic acid diester dibromide.

In the case where a polyvalent carboxylic acid is used as the compound (A), it is necessary to carry out the reaction with the amine compound (B) in the presence of a catalyst, and thus a decatalytic step is required. Further, in the case where hydrazine halide is used as the compound (A), a dehalogenation step is required in the use of the liquid crystal alignment agent. Therefore, from the viewpoint of obtaining a coating film having a small amount of impurities in a small number of steps, the compound (A) used in the synthesis of the polymer (P) can preferably be a polyvalent carboxylic anhydride.

The main skeleton of the polymer (P) differs depending on the monomers (compound (A) and compound (B)) used in the synthesis. Specifically, for example, by using a tetracarboxylic dianhydride as the compound (A) and using an amine compound containing a diamine as the compound (B), it is obtained from polyphthalic acid, polyimine, and polyamine. At least one of the groups consisting of acid esters.

Further, in the case where tetracarboxylic dianhydride is used as the compound (A) and only the compound represented by the formula (1) is used as the compound (B), it is possible to obtain a tetracarboxylic acid derived from the main chain. A polymer of a carbonyl group of an anhydride and a group bonded to a nitrogen atom of the nitrogen-containing hetero ring in the formula (1) (hereinafter also referred to as "specific polymer").

When a tetracarboxylic acid diester or a tetracarboxylic acid diester dihalide is used as the compound (A), and an amine compound containing a diamine is used as the compound (B), a polyphthalate ester can be obtained.

When a dicarboxylic acid or a dicarboxylic acid dihalide halide is used as the compound (A), and an amine compound containing a diamine is used as the compound (B), a polydecylamine can be obtained.

Further, by using the compound (A) and the amine compound (B) as a polymerization of a monomer, a polymer obtained by reacting the compound (A) with the amine compound (B) can be obtained (P) ). The "polymer obtained by reacting the compound (A) with the amine compound (B)" means a step of reacting only the compound (A) with the amine compound (B). The meaning of both the obtained polymer and the polymer obtained by the method including the step of reacting the compound (A) with the amine compound (B).

The polymer (P) contained in the liquid crystal alignment agent of the present invention is preferably selected from the group consisting of polyglycine, polyimine, and a specific polymer, from the viewpoint of improving various characteristics of the liquid crystal alignment film and the liquid crystal display element. And at least one of the group consisting of polyphthalates. That is, the compound (A) is preferably at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide, and more preferably tetracarboxylic acid is used. Diacid anhydride.

(tetracarboxylic dianhydride)

Examples of the tetracarboxylic dianhydride used in the synthesis of the polymer (P) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic butane tetracarboxylic dianhydride: butane tetracarboxylic dianhydride; and alicyclic tetracarboxylic dianhydride: 1, 2, 3, and 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-furanyl)-3-methyl 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3.0] Octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5 :6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclohexane a carboxylic acid dianhydride, a bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc., and an aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc. In addition to this, you can also use This Laid-Open Patent Publication No. tetracarboxylic dianhydride 2010-97188 described. Further, the tetracarboxylic dianhydride used in the synthesis of the polymer (P) may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used in the synthesis of the polymer (P) preferably contains: selected from bicyclo [2.2.1] heptane in terms of the liquid crystal alignment property and the solubility in a solvent. -2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentane Acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan -1,3-diketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-c]furan-1,3-dione, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, 1,2 At least one compound (hereinafter also referred to as "specific tetracarboxylic dianhydride") of a group consisting of 4,5-cyclohexanetetracarboxylic dianhydride and pyromellitic dianhydride. Further, it is preferably a total of tetracarboxylic dianhydride used in the synthesis of the polymer (P). The amount of the specific tetracarboxylic dianhydride used is 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more.

(tetracarboxylic acid diester and tetracarboxylic acid diester dihalide)

The tetracarboxylic acid diester of the compound (A) is, for example, a compound obtained by subjecting the tetracarboxylic dianhydride to ring opening using an alcohol such as methanol, ethanol or propanol. In addition, the tetracarboxylic acid diester dihalide of the compound (A) may be a compound obtained by reacting a tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as sulfinium chloride. A preferred example of the tetracarboxylic dianhydride used to obtain the tetracarboxylic acid diester and the tetracarboxylic acid diester dihalide and the amount used can be explained using the tetracarboxylic acid dianhydride.

[Amine compound (B)]

The amine compound (B) used for the synthesis of the polymer (P) is a compound having at least one of a first-order amine group and a second-order amine group in the molecule. Further, in particular, the liquid crystal alignment agent of the present invention contains the compound represented by the following (1) as the amine compound (B).

Z ¹ -R ¹ -Z ² (1)

(In the formula (1), R ¹ is a divalent organic group; and Z ¹ is a nitrogen-containing heterocyclic ring having a ring number of 5 to 7 having a "-NH-" between carbon-carbon bonds in the ring skeleton of the aliphatic ring. a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted; Z ² is a first-order amine group, -NHR ² (R ² is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and has a R ² group; In the case of an aromatic ring, the aromatic ring is not directly bonded to a nitrogen atom, or a nitrogen-containing heterocyclic ring having a ring number of 5 to 7 between "carbon-carbon bonds" in the ring skeleton of the aliphatic ring. a ring group, the hydrogen atom bonded to the carbon atom of the nitrogen-containing heterocyclic group may be substituted; wherein, in the case where Z ² is "-NHR ² ", Z ² does not directly bond with the aromatic ring of R ¹ Knot.)

Examples of the divalent organic group of R ¹ in the formula (1) include a divalent hydrocarbon group such as a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group, or a divalent hydrocarbon group in the divalent hydrocarbon group. -O-, -COO-, -CO-, - are introduced between at least one of a carbon-carbon bond, a position adjacent to Z ¹ in the formula (1), and a position adjacent to Z ² in the formula (1). A divalent group (except for a divalent group having a hetero ring) having a functional group such as NHCO-, -S-, or -NH-, or a divalent group having a hetero ring. Further, each of these groups may have a substituent such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).

Here, the "hydrocarbon group" in the present specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Further, the "chain hydrocarbon group" means a hydrocarbon group which does not contain a cyclic structure in the main chain but is composed only of a chain structure. Among them, the chain structure may be linear or branched. The "alicyclic hydrocarbon group" means a structure containing only an alicyclic hydrocarbon, and does not contain an aromatic ring structure as a hydrocarbon group of a ring structure. Among them, a hydrocarbon group which does not need to be composed only of a structure of an alicyclic hydrocarbon and which has a chain structure in a part thereof is also included. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary 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.

Specific examples of the divalent hydrocarbon group in the above R ¹ include a methylene group, an ethylidene group, a propane diyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group. Alkanediyl having 1 to 30 carbon atoms such as heptanediyl, octanediyl, nonanediyl, decanediyl, dodecanediyl, tetradecanediyl and eicosyldiyl; A divalent chain unsaturated hydrocarbon group having 1 to 30 carbon atoms such as a propylene group, a butylene group, an ethynyl group or a propargylene group; and these hydrocarbon groups may be linear or branched. In addition, examples of the divalent alicyclic hydrocarbon group include a cyclohexyl group and the like; and examples of the divalent aromatic hydrocarbon group include a stretched phenyl group, a stretched benzyl group, and a phenylethyl group. In addition, examples of the divalent group having a heterocyclic ring include a divalent group in which two hydrogen atoms are removed from a heterocyclic ring such as a piperidine ring or a pyridine ring, and a divalent group including a chain hydrocarbon group and a heterocyclic ring structure, and An alicyclic hydrocarbon structure and a divalent group of a heterocyclic structure.

Z ¹ is a nitrogen-containing heterocyclic group having 5 to 7 ring members in the ring-chain skeleton of the aliphatic ring and having "-NH-" in the ring skeleton of the aliphatic ring, and examples thereof include a piperidine ring and pyrrolidine. A ring structure obtained by removing a hydrogen atom bonded to a carbon atom of a ring such as a ring, a morpholine ring or a hexamethyleneimine ring, or a "-CH substituted with norbornane with "-NH-" ₂ - "A ring structure obtained by removing one hydrogen atom bonded to a carbon atom of the obtained compound. Further, the ring may be substituted with, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like), an alkyl group, an alkoxy group or the like. Among them, Z ¹ is preferably a piperidinyl group, more preferably a 3-piperidinyl group or a 4-piperidinyl group.

R ² of the group "-NHR ² " in Z ² is a monovalent hydrocarbon group having 1 to 15 carbon atoms. Specific examples of R ² include a linear chain such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group or a tetradecyl group. a monovalent chain hydrocarbon group; or a monovalent alicyclic hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclohexylmethyl group, a methylcyclohexyl group, or a norbornyl group; A monovalent aromatic hydrocarbon group such as a phenylmethyl group or a phenylcyclohexyl group. However, if the nitrogen atom of the group "-NHR ² " is directly bonded to the aromatic ring, the reaction of the group "-NHR ² " with the functional group of the compound (A) is difficult to proceed. Therefore, the compound represented by the formula (1) is preferably a compound in which a nitrogen atom of the group "-NHR ² " is not directly bonded to an aromatic ring.

The nitrogen-containing heterocyclic group having 5 to 7 ring members in Z ² may be a description of the nitrogen-containing heterocyclic ring having 5 to 7 ring members in the Z ¹ ring. Wherein R ² in the case of the same, in the case where the group Z ² is "-NHR ^2", it is in view of reactivity with the compound (A) is concerned, it is preferable that this group is not directly bonded to an aromatic ring Knot.

In the group, Z ² is preferably a primary amine group or the nitrogen-containing heterocyclic group.

Preferable specific examples of the compound represented by the formula (1) include a compound represented by the following formula (DA-1) to formula (DA-8), and the like. In addition, hereinafter, compounds represented by the following formulas (DA-1) to (DA-8) are also referred to as "compounds (DA-x) (x is a number corresponding to the formula number) for the sake of convenience) ". In the synthesis of the polymer (P), one type of the compound represented by the formula (1) may be used alone or two or more types may be used in combination.

In the synthesis of the polymer (P), the amine compound (B) may be a compound represented by the above formula (1), but other amines other than the above may be used in combination with the compound.

Examples of the other amine which can be used herein include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples of the amines include, for example, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like. ; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis(cyclohexylamine), and 1,3-bis(aminomethyl)cyclohexane. Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl sulfide. , 4,4'-diaminodiphenylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis ( Trifluoromethyl)-4,4'-diaminobiphenyl, 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)hexafluoropropane, 4,4'-(p-phenylenediphenylene)diphenylamine, 4,4'-(inter)phenylisopropylene Diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 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, N,N'-bis(4-aminophenyl)- Aniline, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5- Diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene , cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy Base-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5 -diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteryloxy-2,4-di Aminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy)chol Decane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzene Methoxyoxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)benzene) 4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4 -diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine-4-carboxylate Acid, 4-(morpholin-4-yl)benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino-ω- Aminophenylalkylene, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine, 1-(4-amino group Phenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indol-6-amine, 4-aminophenyl-4'-aminobenzoic acid ester, 4,4' -[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4-(tetradecyloxy)benzene-1,3-diamine and the following Formula (D-1)

(In the formula (D-1), X ^I and X ^II are a single bond, -O -, - COO- or -OCO-, R ^I is a C 1-3 alkanediyl group, a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, and n is 0 or 1; however, a and b are not 0) at the same time.

Examples of the compound to be represented, and examples of the diamine-based organooxane include 1,3-bis(3-aminopropyl)-tetramethyldioxane, and the like; The diamine described in Japanese Laid-Open Patent Publication No. 2010-97188.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the formula (D-1) is preferably an alkanediyl group having a carbon number of 1 to 3, *-O-, * -COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). Specific examples of the group "-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-nine Alkyl, n-icosyl, and the like. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to other groups.

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

In addition, the other amines used for the synthesis of the polymer (P) may be used alone or in combination of two or more kinds of these compounds in accordance with the driving mode of the liquid crystal display device.

In the synthesis of the polymer (P), the light transmittance of the coating film is improved, or the absorption of the DC voltage is quickly relaxed, the contrast is hard to be lowered, or the printed liquid crystal display element is obtained. The amine compound (B) to be used is preferably a total amount of the amine compound (B) used in the synthesis, and the use ratio of the compound represented by the formula (1) is set to 10 mol% or more. It is preferably 15 mol% or more, particularly preferably 20 mol% or more, and particularly preferably 30 mol% or more. In addition, the use ratio of the compound represented by the formula (1) The upper limit of the example may be appropriately set in accordance with the driving mode of the liquid crystal display element to be applied, etc., and may be within a range of 100 mol% or less based on the total amount of the amine compound (B) used in the synthesis. Ground setting.

When the coating film produced using the liquid crystal alignment agent of the present invention imparts liquid crystal alignment ability by a photo-alignment method, the polymer (P) can be used as a polymer having a photo-alignment structure. Here, the photo-alignment structure refers to a concept including both a photo-alignment group and a decomposable photo-alignment unit. Specifically, the photo-alignment structure may be a group exhibiting photo-alignment by photo-isomerization, photodimerization, photodecomposition, or the like, and examples thereof include a couple containing azobenzene or a derivative thereof as a basic skeleton. a group having a nitrogen benzene group, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing a chalcone or a derivative thereof as a basic skeleton, and a benzophenone-containing group Or a benzophenone-containing group having a basic skeleton as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, and a polyimine or a derivative thereof as a basic skeleton A structure containing a polyimine or the like.

In the case where a polymer having a photo-alignment structure is used as the polymer (P), the polymer (P) is preferably a polymer containing a decomposable photo-alignment portion, and specifically, preferably has a double ring [2.2] .2] a polymer of an octene skeleton or a cyclobutane skeleton. By having such a specific skeleton, the liquid crystal alignment property of the coating film can be further improved. Further, the polymer (P) having the specific skeleton can be, for example, made to contain a cyclobutane tetracarboxylic dianhydride and a bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid. The tetracarboxylic dianhydride of at least one of the dianhydrides is obtained by reacting with an amine compound containing the compound represented by the above formula (1).

In the case of using the photo-alignment method to impart liquid crystal alignment ability to a coating film In the whole amount of the polymer (P) used in the preparation of the liquid crystal alignment agent of the present invention, the use ratio of the polymer having a photo-alignment structure is preferably 10% by weight or more, and more preferably It is 30% by weight to 100% by weight, and particularly preferably 50% by weight to 100% by weight.

[Molecular weight regulator]

In the synthesis of the polymer (P), a terminal-modified polymer can be synthesized together with the compound (A) and the amine compound (B) as described above using a suitable molecular weight modifier. 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 an acid monoanhydride, a monoamine compound, and a monoisocyanate compound. Specific examples of the compound include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecane. a succinic anhydride, n-hexadecyl succinic anhydride or the like; examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like; monoisocyanate Examples of the compound include phenyl isocyanate and 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.

[Synthesis of the compound represented by the formula (1)]

The compound represented by the formula (1) can be synthesized by appropriately combining a common method of organic chemistry. An example of the method is as follows: in the case where Z2 in the formula (1) is a first-order amine group, a nitro intermediate having a nitro group in place of the first-order amine group is synthesized, and then a suitable reduction system is used. The nitro group of the obtained nitro intermediate is aminated method.

The method of synthesizing the nitro intermediate can be appropriately selected depending on the target compound. Examples thereof include a method of protecting a nitrogen-containing heterocyclic ring "-NH-" by using a compound having a nitrogen-containing hetero ring corresponding to Z ¹ and using a suitable protecting group such as a tert-butoxycarbonyl group, and then A method of reacting with a nitro compound having a group corresponding to R ¹ or the like.

The reduction reaction of the nitro intermediate is preferably carried out in an organic solvent, for example, using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin or nickel. The organic solvent used herein may, for example, be ethyl acetate, toluene, tetrahydrofuran or an alcohol. Here, the synthesis procedure of the compound represented by the formula (1) is not limited to the method.

[Synthesis of Polymer (P)]

(Polymeric acid and synthesis of specific polymers)

In the case of synthesizing polyamic acid or a specific polymer as the polymer (P), the use ratio of the tetracarboxylic dianhydride to the amine compound (B) supplied to the synthesis reaction is preferably relative to the amine compound ( B) The amine group which is contained in the amine group is 1 equivalent of the amine group which reacts with the acid anhydride group of the tetracarboxylic dianhydride, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 equivalent to 2 equivalent, and more preferably 0.3 equivalent to 1.2. The ratio of equivalents.

The synthesis reaction of the polyamic acid or the like is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Here, examples of the organic solvent include an aprotic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. As these organic solvents As examples, the aprotic polar solvent may, for example, be N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, γ- Examples of the phenol-based solvent include phenol, m-cresol, xylenol, and halogenated phenol; and examples of the alcohol include methanol, ethanol, and isopropyl. Alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone, etc.; examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, and ethyl ethoxypropionate. , diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate, etc.; ethers, for example, diethyl ether, diisoamyl ether, ethylene glycol methyl ether, ethylene Alcohol ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monomethyl ether acetate, Tetrahydrofuran or the like; examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like; Listed: hexane, heptane, octane, benzene, toluene, xylene, and the like.

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 of a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). 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. The amount of use of the organic solvent (α) is preferably set to be opposite to the opposite The total amount (α + β) of the solution, the total amount (β) of the tetracarboxylic dianhydride and the amine compound (B) is 0.1% by weight to 50% by weight.

As described above, a reaction solution obtained by dissolving polylysine or the like is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be provided by separating the polyamic acid contained in the reaction solution, and then supplied to the preparation of the liquid crystal alignment agent, or may also be used to separate the polylysine. After purification, it is supplied to the preparation of the liquid crystal alignment agent.

[Polyimide as polymer (P)]

The polyimine which is the polymer (P) can be obtained, for example, by subjecting polylysine synthesized in the above manner to dehydration ring closure and imidization.

In the case where polylysine is subjected to dehydration ring closure to form a polyimine, the reaction solution obtained by dissolving the polylysine may be directly supplied to the dehydration ring-closure reaction, or may be a polycondensation contained in the reaction solution. The proline is isolated and then supplied to the dehydration ring closure reaction, or the isolated polylysine may be purified and then supplied to the dehydration ring closure reaction. The isolation and purification of polylysine can be carried out according to a known method.

The polyimine may be a fully ruthenium imide obtained by dehydration ring closure of a proline structure of a polyglycolic acid as a precursor thereof, or may be a part of only a proline structure. A partial quinone imide that dehydrates the ring closure and allows the proline structure to coexist with the quinone ring structure. The polyimine contained in the liquid crystal alignment agent of the present invention preferably has a sulfhydrylation ratio of 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 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 polylysine is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and heating is carried out as needed. Among them, it is preferred to use the latter method.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to a solution of poly-proline, the dehydrating agent may be, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. 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 is exemplified as an organic solvent exemplified as an organic solvent for synthesizing polyamic acid. 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 polyienimine was obtained in the above manner. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent can be removed from the reaction solution and the dehydration ring-closing catalyst can be supplied to the liquid crystal alignment agent, or the polyimine can be isolated and then supplied to the liquid crystal alignment. The preparation of the agent, or the isolated polyimine may also be purified and then supplied 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 can also be obtained by hydrazylation of polyphthalate.

[Polyurethane as polymer (P)]

The polyglycolate (hereinafter also referred to as polyphthalate (P)) as the polymer (P) can be obtained, for example, by the following method: [I] obtained by the synthesis reaction Polymeric (P) polylysine and hydroxyl group-containing compound, halide, containing a method of reacting an epoxy group-containing compound or the like to carry out a reaction; [II] a method of reacting a tetracarboxylic acid diester with an amine compound (B); and [III] a tetracarboxylic acid diester dihalide with an amine compound ( B) A method of carrying out the reaction.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. Further, examples of the halide include methyl bromide, ethyl bromide, octadecyl octadecyl, methyl chloride, chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, and the like. Examples of the compound include propylene oxide and the like. The tetracarboxylic acid diester used in the method [II] and the tetracarboxylic acid diester dihalide used in the method [III] can be used as the compound described in the compound (A). The amine compound (B) used in the method [II] and the method [III] is a compound containing the compound represented by the formula (1), and the other amine may be used as needed. Further, the polyperurate may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

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

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (P) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Further, the molecular weight represented by the ratio of Mw to the polystyrene-converted number average molecular weight (Mn) measured by GPC The distribution (Mw/Mn) is preferably 15 or less, and more preferably 10 or less. By being in the above 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) as described above, but may contain other components as needed. The other component can be appropriately selected depending on the use of the liquid crystal alignment agent. Other components which can be added to the liquid crystal alignment agent of the present invention 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 group"). Compound "), a functional decane compound, a metal chelate compound, a hardening accelerator, a surfactant, and the like.

[Other polymers]

The other polymers may be used to improve solution properties or electrical properties. As the other polymer, for example, polylysine obtained by a reaction of a diamine which does not contain the compound represented by the formula (1) with a tetracarboxylic dianhydride, and a dehydration ring closed by the polyglycolic acid can be used. The obtained polyimine, a polyphthalate obtained by esterification of the polyamic acid, and a reaction of a diamine which does not contain the compound represented by the formula (1) with a dicarboxylic acid are obtained. Polyamide, having polyester, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(methyl) An acrylate or the like as a main skeleton and does not have the polymer of the specific structure. Among them, the other polymer may preferably be at least one selected from the group consisting of polyglycolic acid, polyimine, polyphthalate, and polyoxyalkylene. Further, the polyorganosiloxane may be hydrolyzed, for example, by a hydrolyzable decane compound. Obtained by a condensation reaction. The synthesis of these polymers can be carried out according to a known method.

In the case where other polymers are added to the liquid crystal alignment agent, 100 parts by weight of the total polymer in the composition, and the blending ratio of the other polymer is preferably 50 parts by weight or less, more preferably 0.1 parts by weight to 40 parts by weight, and particularly preferably 0.1 part by weight. 30 parts by weight.

In the case where the liquid crystal alignment agent of the present invention is used for photoalignment, a polymer having a photoalignment structure can be preferably used as the other polymer. Specifically, it is preferably a polymer containing a photo-alignment group, and more preferably a polymer containing a group having a cinnamic acid structure as a photo-alignment group. Among them, a polyorganosiloxane having a cinnamic acid structure can be preferably used as far as the photo-alignment group is easily introduced into the polymer.

Further, the polymer having a photo-alignment group can be synthesized by a conventionally known method. For example, a polyorganosiloxane having a photo-alignment group as another polymer may be a polyorganosiloxane having an epoxy group and a carboxylic acid having a photo-alignment group, preferably an ether, an ester, a ketone, or the like. The reaction is carried out in an organic solvent in the presence of a catalyst such as a 4-stage ammonium salt.

[epoxy group-containing compound]

The epoxy group-containing compound can be used to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. Here, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol 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-aminomethyl Cyclohexane, N, N- A diglycidyl-cyclohexylamine, an epoxy group-containing polyorganosiloxane such as described in International Publication No. 2009/096598, is preferred as a compound.

In the case where the epoxy group-containing compound is added to the liquid crystal alignment agent, the compounding ratio of these epoxy group-containing compounds is preferably 40% by weight based on 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. The amount is preferably from 0.1 part by weight to 30 parts by weight.

[functional decane compound]

The functional decane compound can be used in order to improve the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyl group. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-ureidopropyltrimethoxydecane, N-ethoxycarbonyl-3-amine Propyltrimethoxydecane, N-triethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecane Base-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6- Methyl diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, glycidoxymethyltrimethoxydecane And glycidyloxymethyl triethoxy decane, 2-glycidoxyethyl trimethoxy decane, 3-glycidoxy propyl trimethoxy decane, and the like.

In the case where a 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 or less, more preferably 0.02 part by weight to 0.20 parts by weight based on 100 parts by total of the total of the polymer. Share.

[metal chelate compound]

The metal chelate compound has a ring in a polymer component of a liquid crystal alignment agent In the case of the oxygen structure, it is contained in a liquid crystal alignment agent (especially a liquid crystal alignment agent for a retardation film) for the purpose of ensuring the mechanical strength of the film formed by the low-temperature treatment. The metal chelate compound is preferably an acetonitrile acetone complex or an acetamethylene acetate complex using a metal selected from the group consisting of aluminum, titanium, and zirconium. Specific examples thereof include aluminum diisopropoxyethylacetate, aluminum tris(acetylsulfonate), aluminum tris(ethylacetate), and diisopropoxy bis(ethyl group B). Indoleacetic acid) titanium, titanium diisopropoxy bis(ethyl sulfonate), zirconium tri-n-butoxyethyl acetoacetate, zirconium di-n-butoxy bis(ethyl acetonitrile), and the like. The metal chelate compound is preferably used in an amount of 50 parts by weight or less, more preferably 0.1 parts by weight to 40 parts by weight, even more preferably 1 part by weight, based on 100 parts by weight of the total of the constituent components containing the epoxy structure. Parts ~ 30 parts by weight.

[hardening accelerator]

In the case where the polymer component in the liquid crystal alignment agent has an epoxy structure, the hardening accelerator is contained in the liquid crystal alignment agent in order to ensure the mechanical strength of the formed liquid crystal alignment film and the temporal stability of the liquid crystal alignment property ( In particular, it is a liquid crystal alignment agent for retardation films. As the hardening accelerator, for example, a compound having a phenol group, a stanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group or the like can be used, and among them, a compound having a phenol group or a stanol group is preferable. Specific examples of the compound having a phenol group include cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, and the like; and compounds having a stanol group; For example, trimethyl decyl alcohol, triethyl stanol, 1,1,3,3-tetraphenyl-1,3-dioxane diol, 1,4-bis(hydroxy dimethyl decane) Benzene, triphenyl decyl alcohol, tris(p-tolyl) decyl alcohol, diphenyl decane diol, and the like. The use ratio of the hardening accelerator is preferably 50% by weight based on 100 parts by weight of the total of the constituent components containing the epoxy structure. The amount is preferably from 0.1 part by weight to 40 parts by weight, particularly preferably from 1 part by weight to 30 parts by weight.

[Surfactant]

The surfactant may be contained in a liquid crystal alignment agent (particularly, a liquid crystal alignment agent for a retardation film) for the purpose of improving the coating property of the liquid crystal alignment agent on the substrate. Examples of such a surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, anthrone surfactants, polyalkylene oxide surfactants, and fluorine-containing surface active agents. Agents, etc. The use ratio of the surfactant is preferably 10 parts by weight or less, and more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the liquid crystal alignment agent.

In addition, an antioxidant such as a phenol-based antioxidant or an amine-based antioxidant, or a polyfunctional (meth)acrylate such as ethylene glycol diacrylate or 1,6-hexanediol diacrylate may be added. In the liquid crystal alignment agent.

<solvent>

The liquid crystal alignment agent of the present invention is prepared such that the polymer (P) and other components which are optionally used are preferably a liquid composition obtained by dispersing or dissolving in a suitable solvent.

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylidene, N,N-dimethylformamide, and N,N-dimethyl B. Indoleamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene Alcohol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (Dingsailu), ethylene glycol dimethyl ether, ethylene glycol ether Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene 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) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. 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 as 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, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, and it is difficult to obtain a favorable 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 decreases. tendency.

The range of the particularly preferable solid content concentration differs depending on the use of the liquid crystal alignment agent or the method used when the liquid crystal alignment agent is applied onto the substrate. For example, when the liquid crystal alignment agent for a liquid crystal alignment film is applied to a substrate by a spinner method, the solid content concentration (the total weight of all components other than the solvent in the liquid crystal alignment agent is the total weight of the liquid crystal alignment agent) The ratio in the middle portion is particularly preferably in the range of 1.5% by weight to 4.5% by weight. 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. Also, about In the liquid crystal alignment agent for a retardation film, the solid content concentration of the liquid crystal alignment agent is preferably 0.2% by weight to 10% by weight from the viewpoint of applicability of the liquid crystal alignment agent and the film thickness of the formed coating film. The range is more preferably in the range of 3% by weight to 10% by weight.

<Liquid crystal display element and retardation film>

The liquid crystal alignment film can be produced by using the liquid crystal alignment agent of the present invention described above. In addition, the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention can be preferably applied to a liquid crystal alignment film for a liquid crystal display element and a liquid crystal alignment film for a retardation film. Hereinafter, the liquid crystal display element and the retardation film of the present invention will be described.

[Liquid Crystal Display Element]

The liquid crystal display element of the present invention comprises 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, TN type, STN type, and VA type (including Vertical Alignment-Multidomain Vertical Alignment (VA-MVA) type, vertical Various types of driving methods such as Alignment-Patterned Vertical Alignment (VA-PVA), IPS, FFS, and Optically Compensated Bend (OCB). The liquid crystal display element of the present invention can be produced, for example, by the following steps (I-1) to (I-3). Step (I-1) uses different substrates depending on the desired mode of operation. Step (I-2) and step (I-3) are shared in each operation mode.

[Step (I-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.

(I-1A) In the case of manufacturing, for example, a TN type, STN type or VA type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are used as a pair, and each of the transparent conductive films On the formation 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. As the transparent conductive film provided on one surface of the substrate, a NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), an ITO film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. In order to obtain a patterned transparent conductive film, for example, the following method can be utilized: after forming a transparent conductive film without pattern, pass the light. A method of etching to form a pattern; a method of forming a mask having a desired pattern when forming a transparent conductive film, or the like. 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, a calcination (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 calcination 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. As described above, the film thickness of the formed film is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(I-1B) In the case of manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate including an electrode including a transparent conductive film or a metal film patterned into a comb type is provided, and The liquid crystal alignment agent of the present invention is applied to one surface of the counter substrate of the electrode, 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 (I-1A). As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the above (I-1A) and (I-1B), a coating film to be an alignment film is formed by applying a liquid crystal alignment agent onto a substrate and then removing the organic solvent. In this case, the polymer contained in the liquid crystal alignment agent of the present invention is a poly-proline, or a polyphthalate, or a ruthenium-imided polymer having a quinone ring structure and a proline structure. In the case of forming a coating film, it may be further heated to carry out a dehydration ring-closure reaction to obtain a more imidized coating film.

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

In the case of manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, as a process of imparting a liquid crystal alignment ability to the coating film formed in the above step (I-1), the following rubbing treatment is performed: A roll of a cloth wrapped with fibers such as nylon, rayon, cotton, etc., rubs the coating film in a fixed direction. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. On the other hand, in the case of producing a VA liquid crystal display element, the coating film formed in the above step (I-1) can be directly used as the liquid crystal alignment film, but the coating film may be subjected to a rubbing treatment. Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to a pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays. a process of changing; or after forming a resist film on a portion of the surface of the liquid crystal alignment film, performing a rubbing treatment in a direction different from the previous rubbing treatment, and then removing the resist film; thereby causing the liquid crystal alignment film in each region Have different liquid crystal alignment capabilities. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. Further, 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. The treatment for imparting liquid crystal alignment ability to the coating film may be a treatment using a photo-alignment method instead of the rubbing treatment.

[Step (I-3): Construction of Liquid Crystal Cell]

By preparing two substrates in which the liquid crystal alignment film is formed as described above, liquid crystal cells are formed by disposing liquid crystal between the two substrates arranged in the opposite direction. For the production of the liquid crystal cell, for example, the following two methods are exemplified. 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 respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the cells are divided by the substrate surface and the sealant. After the filling liquid crystal is injected into the gap, the injection hole is sealed, whereby the liquid crystal cell can be manufactured. In addition, the second method is a method called a One Drop Fill (ODF) method. Applying, for example, an ultraviolet curable sealant to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and further adding liquid crystal to a predetermined number of portions on 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, whereby the liquid crystal cell can be manufactured. In the case of using any of the methods, it is preferable to heat the liquid crystal cell produced in the above manner to a temperature at which the liquid crystal to be used becomes an isotropic phase, and then gradually cool to room temperature to remove the liquid crystal filling. Time Flow alignment.

As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. Further, examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, Schiff base liquid crystals and oxidized couples can be used. Azoxy 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. Further, it is also possible to use a liquid crystal such as cholesteric liquid crystal such as cholesteryl chloride, cholesteryl phthalate or cholesteryl carbonate; -15", "CB-15" (manufactured by Merck), a chiral agent; p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate (p- Decroxybenzylidene-p-amino-2-methylbutylcinnamate) and the like ferroelectric liquid crystal (ferroelectric liquid crystal).

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 is a polarizing film obtained by absorbing iodine while extending the polyvinyl alcohol to the side.

[Relativity film]

In the case where the retardation film is produced by using the liquid crystal alignment agent of the present invention, not only dust or static electricity generation can be suppressed in the step, but also a uniform liquid crystal alignment film can be formed, and it can be suitably used by irradiation of radiation. Mask in the base In terms of arbitrarily forming a plurality of regions having different liquid crystal alignment directions, it is preferable to use a photoalignment method. Specifically, it can be produced through the following steps (II-1) to (II-3).

[Step (II-1): Formation of Coating Film Using Liquid Crystal Aligning Agent]

First, the liquid crystal alignment agent of the present invention is applied onto a substrate to form a coating film. The substrate used herein may be suitably exemplified to include cellulose triacetate, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polyamine, polyimine, polymethyl methacrylate A transparent substrate of synthetic resin such as ester or polycarbonate. Among these substrates, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. Further, polymethyl methacrylate can be preferably used as a substrate for a retardation film in terms of low hygroscopicity of the solvent, good optical properties, and low cost. Further, in order to make the substrate for coating the liquid crystal alignment agent more excellent in adhesion between the surface of the substrate and the coating film, a conventionally known pretreatment may be performed on the surface on which the coating film is formed on the surface of the substrate.

In most cases, the retardation film is used in combination with a polarizing film. At this time, in order to exhibit desired optical characteristics, it is necessary to precisely control the angle of the polarizing film with respect to the polarization axis to a specific direction to bond the retardation film. Therefore, by forming a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle on a substrate such as a TAC film or a polymethyl methacrylate, it is possible to omit the retardation film while controlling the angle thereof. The step on the polarizing film. In addition, it is thereby possible to contribute to improvement in productivity of the liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle, it is preferably carried out by a photoalignment method using the liquid crystal alignment agent of the present invention.

The coating of the liquid crystal alignment agent on the substrate can be carried out by a suitable coating method. For example, the following methods can be employed: a roll coater method, a spinner method, a printing method, an inkjet method, Bar coater method, extrusion die method, direct gravure coater method, chamber doctor coater method, offset gravure coater Method, single roll kiss coater method, reverse kiss coater method using small-diameter gravure roll, 3 trans-roll coater method, 4 anti-coating method Roll coater method, slot die method, air knife coater method, positive rotary roll coater method, blade coater method, knife coater method, impregnation coating Machine method, MB coater method, MB trans coater method, etc.

After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, and more preferably 80 to 140 ° C. The heating time is preferably from 0.1 minute to 15 minutes, and more preferably from 1 minute to 10 minutes. The film thickness of the coating film formed on the substrate is preferably from 1 nm to 1,000 nm, and more preferably from 5 nm to 500 nm.

[Step (II-2): Light irradiation step]

Then, the coating film formed on the substrate in the above manner is irradiated with light to impart a liquid crystal alignment ability to the coating film. Here, examples of the light to be irradiated include ultraviolet rays, visible rays, and the like which include light having a wavelength of 150 nm to 800 nm. Among these lights, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. The illumination light may be polarized or non-polarized. The polarized light is preferably a light containing linearly polarized light.

When the light to be used is polarized, when the light is irradiated, the substrate surface may be irradiated from a vertical direction, or may be irradiated from an oblique direction, or these irradiations may be combined. In the case of irradiating non-polarized light, it is necessary to irradiate the substrate surface from the direction of tilt.

Examples of the light source to be used include a low pressure mercury lamp and a high pressure mercury lamp. Xenon lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps (Hg-Xe lamps), and the like. The polarized light can be obtained by a method in which these light sources are used in combination with, for example, a filter, a diffraction grating, or the like.

The amount of light irradiation is preferably 0.1 mJ/cm ² or more and less than 1,000 mJ/cm ² , more preferably 1 mJ/cm ² to 500 mJ/cm ² , and particularly preferably ² mJ/cm ² to 200 mJ/cm. ² .

[Step (II-3): Formation of liquid crystal layer]

Then, the polymerizable liquid crystal is applied and cured on the coating film which has been subjected to light irradiation as described above. Thereby, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used herein is a liquid crystal compound or a liquid crystal composition which is polymerized by at least one of heating and light irradiation. As the polymerizable liquid crystal, a conventionally known liquid crystal can be used. Specifically, for example, Non-Patent Document 1 ("UV-Curable Liquid Crystals and Their Application", "Liquid Crystal", The nematic liquid crystal described in Volume 3 (1999), pages 34 to 42). Further, it may be: a cholesteric liquid crystal; a disc-shaped liquid crystal; a twisted nematic alignment type liquid crystal to which a chiral agent is added. The polymerizable liquid crystal may also be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may also be a composition further containing a known polymerization initiator or a suitable solvent.

In order to apply the polymerizable liquid crystal as described above to the coating film formed using the liquid crystal alignment agent, for example, a bar coater method, a roll coater method, a spinner method, a printing method, an inkjet method, or the like may be employed. Coating method.

Then, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from the group consisting of heating and light irradiation to cure the coating film to form a liquid crystal layer. These treatments are carried out by overlapping, and it is preferable since a good alignment is obtained.

The heating temperature of the coating film can be appropriately selected depending on the type of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferable to carry out heating at a temperature in the range of 40 to 80 °C. The heating time is preferably from 0.5 minutes to 5 minutes.

As the irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light irradiation is preferably 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 5,000 mJ/cm ² .

The thickness of the formed liquid crystal layer is appropriately set in accordance with desired optical characteristics. For example, in the case of producing a 1/2 wavelength plate of visible light having a wavelength of 540 nm, the phase difference of the formed retardation film is selected to be a thickness of 240 nm to 300 nm, and when it is a quarter wave plate, the phase difference is selected to be 120 nm. 150 nm thickness. The thickness of the liquid crystal layer which obtains the target phase difference differs depending on the optical characteristics of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for producing a quarter-wave plate is in the range of 0.6 μm to 1.5 μm.

The retardation film obtained in the above manner can be preferably used as a retardation film of a liquid crystal display element. The liquid crystal display element of the retardation film produced by using the liquid crystal alignment agent of the present invention is not limited in its driving method, and can be applied to various known methods such as TN type, STN type, IPS type, FFS type, and VA type. The retardation film is used by attaching a surface on the substrate side of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable that the substrate of the retardation film is made of TAC or an acrylic substrate, and the substrate of the retardation film also functions as a protective film of the polarizing film.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for: clocks, portable games, word processors (word Processor), note type personal computer, car navigation system, camcorder, personal digital assistant (PDA), digital camera, mobile phone, smart phone, various surveillance Various display devices such as a liquid crystal television, an information display, and the like.

[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 and synthesis examples, the weight average molecular weight Mw of the polymer, the oxime imidization ratio, the epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods.

[weight average molecular weight Mw of polymer]

Mw is a polystyrene-converted value measured by gel permeation chromatography under the following conditions.

Pipe column: manufactured by Tosoh (stock), TSKgel GRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

[Polylination rate of polymer]

The solution containing the polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, using tetramethyl decane as a reference substance at room temperature. measured at ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR). From the obtained ¹ H-NMR spectrum, the oxime imidization ratio was determined using the following formula (1).

醯 imidization rate (%) = (1-A ¹ /A ² ×α)×100...(1)

(Equation (1), A ¹ is the peak area derived from proton of NH group in the vicinity of a chemical shift of 10ppm appear, A ² is the peak area derived from other protons, α with respect to the other protons precursor polymer The ratio of the number of protons of the NH group in (polyglycine).)

[epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solid viscosity of polymer solution]

The solution viscosity (mPa.s) of the polymer solution was measured at 25 ° C using an E-type rotational viscometer.

<Synthesis of Amine Compounds>

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

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

Mix in a 1000 mL three-necked flask equipped with a thermometer and a three-way cock 64.6 g (0.5 mol) of 4-carboxypiperidine, 163.7 g (0.75 mol) of di-tert-butyl dicarbonate, and 500 mL of tetrahydrofuran (THF) were stirred at 25 ° C for 10 minutes. After adding 18.3 g (0.15 mol) of N,N-dimethylaminopyridine (DMAP), the reaction was carried out by stirring at 25 ° C for 4 hours. Then, after mixing with 500 mL of ethyl acetate, it was liquid-separated by sodium bicarbonate aqueous solution and distilled water. The organic layer was concentrated and dried to give 69.3 g of Intermediate (DA-1-1).

Next, 69.3 g of the intermediate (DA-1-1), 46.1 g of 4-nitrophenol, and 600 mL of dichloromethane were stirred and mixed in an ice bath in a 2 L three-necked flask. Then, 186.9 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and N,N-dimethylaminopyridine (DMAP) 1.2 were sequentially introduced. g, reacted in an ice bath for 1 hour, and then reacted at room temperature for 4 hours. After the reaction, 100 mL of trifluoroacetic acid was added, and after mixing with 500 mL of ethyl acetate, the liquid separation was carried out by using distilled water. Then, the organic layer was concentrated to precipitate a solid. The precipitated solid was collected by filtration, washed thoroughly with ethanol, and dried to obtain 65.2 g of a nitro intermediate (DA-1-2).

Then, 65.2 g of the nitro intermediate (DA-1-2), 7 g of 5% Pd/C, 250 mL of ethanol, and 250 mL of tetrahydrofuran were added to a 2 L three-necked flask under a nitrogen stream, and then replaced with hydrogen in hydrogen. In the presence of the reaction, the reaction is carried out at room temperature. The reaction was traced by high performance liquid chromatography (HPLC), and it was confirmed that the reaction was carried out and then filtered. The filtrate was mixed with 3000 mL of ethyl acetate, and then subjected to liquid separation purification using 200 mL of distilled water. The organic layer was distilled under reduced pressure to remove a solvent, whereby a solid was precipitated. 52.3 g of the compound (DA-1) was obtained by recrystallizing the precipitated solid from ethanol.

<Synthesis of Polymer>

[Example 2-1; Synthesis of Polymer (PA-1)]

34.95 g (98 moles) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and 40.05 g (100 moles) of compound (DA-1) as an amine compound The fraction was dissolved in 425 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 ° C for 10 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure, whereby a polymer (PA-1) was obtained. The obtained polymer (PA-1) was prepared to 10% by weight using NMP, and the viscosity of the solution was measured and found to be 1250 mPa. s. Further, the polymer solution was allowed to stand at 20 ° C for 3 days, and as a result, it was not gelated, and the storage stability was good.

[Example 2-2 to Example 2-7 and Synthesis Example 1 to Synthesis Example 3; Synthesis of Polymer (PA-2) to Polymer (PA-10)]

A polymer was obtained in the same manner as in Example 2-1, except that the type and amount of the tetracarboxylic dianhydride and the amine compound used in the reaction were as shown in Table 1 below. The viscosity of a 10% by weight polymer solution prepared by using NMP is shown together in Table 1 below. Further, regarding the tetracarboxylic dianhydride, the numerical values in Table 1 indicate the use ratio (mol%) relative to the total amount of the tetracarboxylic dianhydride used in the reaction, and regarding the amine compound, the numerical values in Table 1 are relative to The ratio of use of the total amount of the amine compound used in the reaction (% by mole). The polymer solutions obtained in the examples were each allowed to stand at 20 ° C for 3 days, and as a result, they were not gelled, and the storage stability was good.

(Compound (A))

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

AN-2: pyromellitic dianhydride

AN-3: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

AN-4: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride

AN-5: 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3 -dione

(Compound (B))

DA-4: a compound represented by the following formula (d-4)

DA-5: 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine

DA-6: p-phenylenediamine

DA-7: 4,4'-diaminodiphenylmethane

DA-8: 4-aminophenyl-4'-aminobenzoate

DA-9: 2,4-diamino-N,N-diallylaniline

DA-10: 4,4'-diaminodiphenylamine

DA-11: 3,5-diaminobenzoic acid

DA-12: 3,5-diaminobenzoic acid cholesteryl ester

DA-13: 4-(tetradecyloxy)benzene-1,3-diamine

[Example 2-8: Synthesis of Polymer (PI-1)]

22.55 g (98 moles) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 2.22 g (20 mole parts) of p-phenylenediamine as an amine compound, 4 -aminophenyl-4'-aminobenzoate 7.03 g (30 mole parts), and compound (DA-3) 18.20 g (50 mole parts) dissolved in N-methyl-2-pyrrolidone ( In NMP) 283.3 g, the reaction was carried out at 60 ° C for 6 hours. Then, 166.7 g of NMP was added, 15.92 g of pyridine and 20.54 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 100 ° C for 8 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain a polyimine having a ruthenium iodide ratio of about 50% (referred to as "polymer (PI-1). )"). The obtained polymer (PI-1) was prepared to 10% by weight using NMP. The viscosity of the solution was measured and found to be 980 mPa. s. In addition, the gathering The solution was allowed to stand at 20 ° C for 3 days, and as a result, it was not gelled, and the storage stability was good.

[Synthesis Example 4: Synthesis of a polymer using piperazine]

6.948 g (100 mol parts) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and 3.052 g (100 mol parts) of piperazine were dissolved in 90 g of NMP. The reaction was carried out for 24 hours at room temperature. A small amount of the reaction solution was taken, and the viscosity of the solution was measured, and the result was 17 mPa. s. Therefore, the reaction was further carried out at 60 ° C for 24 hours, and the solution viscosity was 18 mPa. s. Therefore, the reaction mixture was poured into a large amount of excess methanol, and the reaction product was precipitated, but only white turbid and not solidified, and the polymer could not be obtained.

[Synthesis Example 5: Synthesis of polyorganosiloxane (S-1)]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone, and three to three were charged. 10.0 g of the amine was mixed at room temperature. Thereto, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then mixed under reflux, and the reaction was carried out at 80 ° C for 6 hours. After the completion of the reaction, the organic layer was taken out, and the organic layer was washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, thereby being a viscous transparent liquid. The form of a polyorganosiloxane having an oxopropyl group is obtained. For ¹ H- NMR ^{(1 H-Nuclear Magnetic Resonance,} 1 H-NMR) analysis, the results in the vicinity of a chemical shift (δ) = 3.2ppm, as the theoretical strength of the silicon oxide alkoxy polyorganosiloxane having an oxetanyl propyl A peak based on the oxirane group was obtained, and a side reaction in which no oxyheteropropyl group was produced in the reaction was confirmed. The epoxy equivalent of the polyorganosiloxane having an oxiranyl group was measured and found to be 186 g/eq.

Then, 9.3 g of the obtained polyorganosiloxane having an oxopropyl group, 26 g of methyl isobutyl ketone, and 4-phenoxy group were placed in a 100 mL three-necked flask. 3 g of cinnamic acid and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) were reacted at 80 ° C for 12 hours while stirring. After completion of the reaction, the reaction mixture was poured into methanol, and the resulting precipitate was collected, and the precipitate was dissolved in ethyl acetate to prepare a solution. After washing the solution three times, the solvent was distilled off, thereby In the form of a white powder, 6.3 g of a polyorganosiloxane (S-1) having an oxiranyl group and a liquid crystal-aligning group was obtained. The polystyrene-equivalent weight average molecular weight Mw measured by the gel permeation chromatography of the polyorganosiloxane (S-1) was 3,500.

<Preparation and evaluation of liquid crystal alignment agent>

[Example 3-1: FFS type liquid crystal display element]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-1) obtained in Example 2-1 was dissolved in a mixed solvent containing γ-butyrolactone (GBL), NMP, and Dicasso (BC) (GBL: NMP: BC = In 40:40:20 (weight ratio), a solution having a solid concentration of 4.0% by weight was prepared. This solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of coating properties

The prepared liquid crystal alignment agent was applied onto a glass substrate by a spinner, prebaked on a hot plate at 80 ° C for 1 minute, and then heated in a 200 ° C oven in which nitrogen was replaced in the chamber (post-baking) Bake) for 1 hour, thereby forming a coating film having an average film thickness of 1,000 Å. The coating film was observed with a microscope having a magnification of 20 times, and the film thickness unevenness and the presence or absence of pinholes were ascertained. The evaluation was carried out in such a manner that the film thickness unevenness and the pinhole were not observed, and the coating property was evaluated as "good", and at least one of the film thickness unevenness and the pinhole was clearly observed. The situation of the person is evaluated as "coating" Good. In this example, neither the film thickness unevenness nor the pinhole was observed, and the film coating property was "good".

(3) Evaluation of light transmittance

With respect to the obtained coating film, a light transmittance (%) at a wavelength of 400 nm was evaluated using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.). The evaluation was performed in such a manner that 97% or more of the cases was evaluated as "good" light transmittance, and when it was less than 97%, light transmittance "bad" was evaluated. As a result, the coating film was 99.1%, and the light transmittance was "good".

(4) Evaluation of friction resistance

With respect to the obtained coating film, a rubbing machine having a roll with a cotton cloth was used, and rubbing treatment was performed five times at a roll rotation speed of 1000 rpm, a table moving speed of 20 cm/sec, and a hair press-in length of 0.4 mm. The foreign matter (fragment of the coating film) caused by the friction removal on the obtained substrate was observed with an optical microscope, and the number of foreign matter in a region of 500 μm × 500 μm was calculated. The evaluation was carried out in such a manner that the case where the number of foreign matter was 5 or less was evaluated as "good" in abrasion resistance, and the case of 6 or more and 9 or less was evaluated as "may", and 10 or more cases were evaluated as resistant. Frictional "bad". As a result, the abrasion resistance of the coating film was "good".

(5) Evaluation of orientation

For the obtained glass substrate with the alignment film subjected to the rubbing treatment (alignment treatment), a refractive index anisotropy (delay) was measured using a liquid crystal alignment film inspection apparatus (LayScan) manufactured by Moritex Co., Ltd. (nm)). The evaluation was carried out in such a manner that the measurement result of the refractive index anisotropy was 0.025 nm or more, and the alignment property was "good", and the case of less than 0.025 nm was evaluated as the "defective" alignment property. As a result, the substrate was 0.036 nm, and the alignment property was "good".

(6) Manufacture of FFS type liquid crystal display elements

The FFS type liquid crystal display element shown in Fig. 1 was produced. First, a pair of glass substrates 11a having two system electrode pairs on one side and a counter glass substrate 11b not provided with electrodes are formed as a pair, and the two system electrode pairs are sequentially formed with a bottom electrode 12 having no pattern as an insulating layer. The tantalum nitride film 13 and the upper electrode 14 patterned into a comb shape are coated on the surface of the glass substrate 11a having the electrode and the surface facing the glass substrate 11b by using a rotator to respectively apply the prepared liquid crystal. An alignment agent forms a coating film. Then, the coating film was prebaked on a hot plate at 80 ° C for 1 minute, and then heated (post-baked) at 230 ° C for 15 minutes in an oven purged with nitrogen in the chamber to form an average film thickness of 1,000 Å. Coating film. A schematic plan view of the upper electrode 14 is shown in FIG. 2(a) is a plan view of the upper electrode 14, and FIG. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2(a). In the present embodiment, a substrate having an upper electrode having a line width d1 of 4 μm and a distance d2 between electrodes of 6 μm is used.

Then, each surface of the coating film formed on the glass substrate was subjected to a rubbing treatment in the direction of the arrow in (b) of FIG. 2 by using cotton. These substrates were bonded to each other with a spacer having a diameter of 3.5 μm so that the mutually rubbing directions of the substrates were anti-parallel, and liquid crystal MLC-6221 (manufactured by Merck) was injected. Further, the polarizing plate is bonded to the outer surfaces of the substrate so that the polarization directions of the two polarizing plates are orthogonal to each other, whereby the liquid crystal display element 10 is produced.

(7) Evaluation of liquid crystal alignment

For the manufactured FFS type liquid crystal display element, use a microscope to observe when the magnification is 50 times. Turns off (ON.OFF) (applies.releases) the presence or absence of an abnormal area in the change in brightness and darkness at a voltage of 5V. The evaluation is carried out as follows: will not be observed In the case of the abnormal region, the liquid crystal alignment property was evaluated as "good", and the case where the abnormal region was observed was evaluated as the liquid crystal alignment "bad". The liquid crystal alignment property in the liquid crystal display element is "good".

(8) Evaluation of voltage retention rate

With respect to the manufactured FFS-type liquid crystal display device, after applying a voltage of 5 V at an application time of 60 μsec and a span of 167 msec at 23 ° C, the voltage holding ratio (VHR) after 167 msec from the application release was measured, and the result was measured. The voltage holding ratio was 99.4%. Further, VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(9) Evaluation of heat resistance

The voltage holding ratio was measured in the same manner as in the above (8), and its value was taken as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 100 ° C for 500 hours. Then, the liquid crystal display element was allowed to stand at room temperature and left to cool to room temperature, and then the voltage holding ratio (VHR _AF ) was measured in the same manner as described above. Moreover, the rate of change of the voltage holding ratio (ΔVHR (%)) before and after the application of the thermal stress is obtained by the following formula (2).

△VHR(%)=((VHR _BF -VHR _AF )÷VHR _BF )×100...(2)

The evaluation of the heat resistance was carried out by evaluating the case where the rate of change ΔVHR was less than 4% as "excellent" in heat resistance, and the case of 4% or more and less than 5% as "good", and the case of 5% or more. It was evaluated as "poor" in heat resistance. As a result, ΔVHR was 2.9%, and the heat resistance of the liquid crystal display element was "excellent".

(10) Contrast evaluation after driving stress (evaluation of AC afterimage characteristics)

In the FFS-type liquid crystal display device manufactured as described above, after being driven by an alternating current voltage of 10 V for 30 hours, a device in which a polarizer and an analyzer are disposed between a light source and a light amount detector is used to measure the expression represented by the following formula (3). Minimum relative transmittance (%).

Minimum relative transmittance (%) = (β - B ⁰ ) / (B ¹⁰⁰ - B ⁰ ) × 100 (3)

(In the formula (3), B ⁰ is the amount of light transmitted under the crossed Nicols in the blank state; B ¹⁰⁰ is the amount of light transmitted under the parallel Nicols in the blank state; β is Under a crossed Nicols, the liquid crystal display element is sandwiched between the polarizer and the analyzer to achieve a minimum amount of light transmission.)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level in the dark state in the FFS type display element, the more excellent the contrast. The case where the minimum relative transmittance was less than 0.5% was evaluated as "good", the case where 0.5% or more and less than 1.0% was evaluated as "OK", and the case where 1.0% or more was evaluated as "poor". As a result, the minimum relative transmittance of the liquid crystal display element was 0.3%, and it was judged as "good".

(11) Evaluation of the relaxation rate of residual direct current (DC) (evaluation of DC afterimage characteristics)

For the liquid crystal display device to be manufactured, a 6504C liquid crystal physical property evaluation device manufactured by Toyo Konica Corporation was used, and the relaxation rate of residual DC was measured by a dielectric absorption method. The measurement was carried out in an environment of 60 ° C, and after applying a DC voltage of 10 V for 30 minutes, the battery was discharged for 1 second, and then the residual DC was measured for 30 minutes. The relaxation rate of the residual DC is calculated by calculating the average residual DC mitigation based on the maximum value of the residual DC and the residual DC value after 1 minute of the time at which the maximum value is displayed. Calculated by speed. The evaluation was performed in such a manner that the relaxation rate of the residual DC was 4 mV/sec or more, and the residual DC relaxation property was "excellent", and the case of 2 mV/sec or more and less than 4 mV/sec was evaluated as the residual DC relaxation property. The case where the temperature was less than 2 mV/sec was evaluated as "defective" in the residual DC relaxation property. Further, the faster the relaxation speed, the more difficult it is to generate an afterimage, and the better the afterimage characteristics are. The relaxation rate of the residual DC of the liquid crystal display element of the present embodiment was 4.9 mV/sec, and it was judged that the residual DC relaxation property was "excellent".

[Example 3-2 to Example 3-7 and Comparative Example 1 to Comparative Example 3]

A liquid crystal alignment agent was prepared in the same manner as in Example 3-1 except that the polymer shown in the following Table 2 was used as the polymer, and an FFS type liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 2 below.

As shown in Table 2, in Examples 3-1 to 3-4, Examples 3-6 and 3-7, the coating properties of the liquid crystal alignment agent, the light transmittance of the coating film, and the abrasion resistance were The alignment property, and the liquid crystal alignment property, the voltage holding ratio, the heat resistance, the contrast after the driving stress, and the relaxation rate of the residual DC of the liquid crystal display element were all "good" or "excellent". Further, in Example 3-5, except that the contrast after the driving stress was "OK", the others were all "good" or "excellent". On the other hand, in Comparative Example 1, the evaluation of the alignment property of the coating film, the heat resistance of the liquid crystal display element, and the contrast after the driving stress was "poor", and the residual DC relaxation speed was inferior to that of the examples. Further, in Comparative Example 2, the light transmittance was "poor", and in Comparative Example 3, the relaxation rate of the residual DC was "poor".

[Example 3-8: TN type liquid crystal display element]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-7) obtained in Example 2-7 as a polymer was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50:50 (weight ratio)) to prepare a solid component. A solution having a concentration of 6.5% by weight. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

The liquid crystal alignment agent prepared in the above (1) was applied to a transparent electrode surface of a glass substrate having a transparent electrode including an ITO film at a temperature of 80 ° C using a liquid crystal alignment film printer (manufactured by Nippon Photographic Co., Ltd.). The hot plate was preheated (prebaked) for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. The coating film was observed with a microscope having a magnification of 20 times to find uneven printing and the presence or absence of pinholes. The evaluation was performed in such a manner that the unevenness of printing and the pinholes were not observed as the printability. "Good", it was evaluated that a small amount of printing unevenness and at least one of the pinholes were evaluated as "printability", and it was evaluated that a large amount of printing unevenness and at least one of pinholes were observed as Printability is "bad". In the present embodiment, neither printing unevenness nor pinholes were observed, and the printability was "good".

(3) Manufacture of TN type liquid crystal cell

The liquid crystal alignment agent prepared in the above (1) was applied to a transparent electrode surface of a glass substrate having a transparent electrode including an ITO film at a temperature of 80 ° C using a liquid crystal alignment film printer (manufactured by Nippon Photographic Co., Ltd.). The hot plate was preheated (prebaked) for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. The coating film was subjected to a rubbing treatment using a rubbing machine having a roll wound with a rayon cloth at a roll rotation speed of 500 rpm, a table moving speed of 3 cm/sec, and a hair press-in length of 0.4 mm to impart liquid crystal alignment ability. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. Further, the above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film.

Next, after an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, the pair of substrates is The liquid crystal alignment film faces are overlapped and crimped to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck & Co., MLC-6221) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed by an acrylic photocurable adhesive, thereby manufacturing a TN type liquid crystal cell. .

(4) Evaluation of liquid crystal alignment

For the liquid crystal cell fabricated in the above (3), under a crossed Nicol prism, using a microscope, the magnification is 50 times to observe when turned on. Abnormal area when 5V is disconnected Whether there is. The evaluation was carried out in the same manner as (7) of the above Example 3-1. As a result, the liquid crystal alignment property in the liquid crystal display element was "good".

(5) Evaluation of pretilt stability

With respect to the liquid crystal cell produced in the above (3), the tilt angle of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using a He-Ne laser, and this value was defined as an initial pretilt angle (θ _IN ). The crystal rotation method is based on Non-Patent Document 1 (TJ Scheffer et al., Journal of Applied Physics, J. Appl. Phys., Vol. 48, p. 1783 (1977)) and Non-Patent Document 2 (F). The method described in "Nakhano et al., Japanese Journal of Applied Physics (JPN. J. Appl. Phys.), Vol. 19, p. 2013 (1980)).

Then, the liquid crystal pretilt angle measured initial (θ _IN) of the display element 5V AC voltage is applied for 100 hours. Then, the pretilt angle was measured again in the same manner as described above, and this value was taken as the pretilt angle (θ _AF ) after the voltage application. These measured values were substituted into the following formula (4), and the amount of change in the pretilt angle (Δθ (°)) before and after the voltage application was obtained.

Δθ=| θ _AF -θ _IN |...(4)

When the Δθ is less than 3%, the pretilt stability is evaluated as “excellent”, the case where 3% or more and less than 4% is evaluated as the pretilt stability “good”, and the case where 4% or more is evaluated as the pretilt stability. "Poor", as a result, the pretilt change rate of the liquid crystal display element was 2.6%, and it was judged that the pretilt stability was "excellent".

(6) Evaluation of heat resistance

The voltage holding ratio (VHR _BF ) was measured in the same manner as (8) of the above Example 3-1, and the voltage before and after the heat stress was given in the same manner as (9) of the embodiment 3-1. The heat resistance was evaluated by the rate of change of the retention ratio ΔVHR. As a result, the initial voltage holding ratio VHR _BF was 99.1%. Further, ΔVHR was 2.8%, and it was judged that the heat resistance was "excellent".

[Example 3-9: VA type liquid crystal display element]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-6) obtained in Example 2-6 as a polymer was added to NMP and BC to have a solid concentration of 6.5% by weight and a solvent mixture ratio of NMP:BC=50: 50 (by weight) solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

Using the liquid crystal alignment agent prepared in the above (1), the printability was ascertained in the same manner as (2) of the above Example 3-8, and as a result, uneven printing and pinholes were not observed. The printability is "good".

(3) Manufacture of VA type liquid crystal cell

The prepared liquid crystal alignment agent was applied onto a transparent electrode surface of a glass substrate (thickness: 1 mm) having a transparent electrode containing an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The plate was heated (prebaked) for 1 minute on a hot plate at 80 ° C, and further heated (post-baked) on a hot plate at 200 ° C for 60 minutes to form a coating film (liquid crystal alignment film) having an average film thickness of 800 Å. This operation was repeated to obtain a pair of (two pieces) glass substrates having a liquid crystal alignment film on the transparent conductive film.

Next, the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film is coated with an epoxy resin to which an alumina ball having a diameter of 5.5 μm is applied. After the agent, the pair of substrates are superposed and pressure-bonded so that the liquid crystal alignment film faces are opposed to each other to harden the adhesive. Then, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) 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 produce a VA liquid crystal cell.

(4) Evaluation of liquid crystal alignment and heat resistance

In the liquid crystal cell produced in the above (3), the liquid crystal alignment property was evaluated in the same manner as in (4) of Example 3-8, and as a result, the liquid crystal alignment property of the liquid crystal display device was "good". Further, the voltage holding ratio (VHR _BF ) was measured in the same manner as (8) of Example 3-1, and the voltages before and after the heat stress were applied in the same manner as (9) of the above Example 3-1. The heat resistance was evaluated by the rate of change of the retention ratio ΔVHR. As a result, the initial voltage holding ratio VHR _BF was 99.4%. Further, ΔVHR was 2.9%, and it was judged that the heat resistance was "excellent".

[Example 3-10: retardation film]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-2) obtained in Example 2-2 and 5 parts by weight of the polyorganosiloxane (S-1) obtained in Synthesis Example 5 were dissolved in a mixed solvent containing NMP and BC ( In NMP: BC = 50:50 (weight ratio), a solution having a solid concentration of 3.5% by weight was prepared. This solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Fabrication of retardation film

The prepared liquid crystal alignment agent was applied to one surface of the TAC film as a substrate by using a bar coater, and baked at 120 ° C for 2 minutes in an oven to form a coating film having a film thickness of 100 nm. Then, on the surface of the coating film, a polarized ultraviolet ray of 10 mJ/cm ² containing an open line of 313 nm was vertically irradiated from the substrate normal line using an Hg-Xe lamp and a Glan Taylor prism to form a liquid crystal alignment film. Then, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered using a filter having a pore size of 0.2 μm, and then the polymerizable liquid crystal was applied onto the liquid crystal alignment film by a bar coater to form a polymerizability. Liquid crystal coating film. After baking in an oven adjusted to a temperature of 50 ° C for 1 minute, a non-polarized ultraviolet ray of 1,000 mJ/cm ² containing a bright line of 365 nm was irradiated from the vertical direction using a Hg-Xe lamp to make a polymerizable liquid crystal. The liquid crystal layer is formed by hardening, thereby producing a retardation film.

(3) Evaluation of liquid crystal alignment

In the retardation film produced in the above (2), the liquid crystal alignment property was evaluated by observing the presence or absence of an abnormal region by visual observation under a crossed Nicols and a polarizing microscope (magnification: 2.5 times). The evaluation was carried out in such a manner that the alignment was good under visual observation, and the case where no abnormal region was observed under a polarizing microscope was evaluated as "excellent" in liquid crystal alignment; no abnormal region was observed under visual observation, but in a polarizing microscope The case where the abnormal region was observed was evaluated as "good" for the liquid crystal alignment property, and the case where the abnormal region was observed under both the visual observation and the polarizing microscope was evaluated as the liquid crystal alignment "defect". As a result, the retardation film was evaluated as "excellent" in liquid crystal alignment.

(4) Adhesion

The adhesion of the liquid crystal alignment film to the substrate was evaluated using the retardation film produced in the above (2). First, a spacer having a spacer was used, and a slit was cut from the surface on the liquid crystal layer side of the retardation film by a dicing blade to form 10 × 10 lattice patterns. The depth of each slit is from the surface of the liquid crystal layer to the midpoint of the thickness of the substrate. Then, after adhering to the cellophane tape so as to cover the entire surface of the lattice pattern, the cellophane tape is peeled off. The notch portion of the lattice pattern after peeling was observed by visual observation under crossed Nicols, and the adhesion was evaluated. The evaluation is conducted as follows: The case where the peeling was not confirmed at the intersection of the portion along the incision line and the lattice pattern was evaluated as "excellent"; the number of the lattices observed to be peeled off in the portion was smaller than the number of the entire lattice pattern. In the case of 15%, it was evaluated that the adhesion was "good", and the number of the lattices in which the peeling was observed in the portion was 15% or more in the case where the number of the lattice patterns was 15% or more. As a result, the retardation film was "excellent" in adhesion.

10‧‧‧Liquid display components

11a, 11b‧‧‧ glass substrate

12‧‧‧ bottom electrode

13‧‧‧ nitride film

14‧‧‧Upper electrode

15a, 15b‧‧‧Liquid alignment film

Claims (11)

A liquid crystal alignment agent comprising a polymer obtained by using a compound (A) and an amine compound (B) as a monomer, the compound (A) being selected from the group consisting of a polycarboxylic acid, a polycarboxylic acid anhydride, and a polycarboxylic acid. At least one of a group consisting of a partial esterified product of a polycarboxylic acid and a hydrazine halide of the partial esterified product, the amine compound (B) comprising a compound represented by the following formula (1): Z ¹ - R ¹ -Z ² (1) In the formula (1), R ¹ is a divalent organic group; and Z ¹ is a ring member number having "-NH-" between carbon-carbon bonds in the ring skeleton of the aliphatic ring. a nitrogen-containing heterocyclic group of ~7, wherein a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted; Z ² is a first-order amine group, -NHR ² , or in a ring skeleton of an aliphatic ring; Between the carbon-carbon bonds, a nitrogen-containing heterocyclic group having a ring number of 5 to 7 of "-NH-", a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted, and R ² is carbon a monovalent hydrocarbon group of 1 to 15 in which the aromatic ring is not directly bonded to a nitrogen atom in the case where R ² has an aromatic ring; wherein, in the case where Z ² is "-NHR ² ", Z ² does not react with R having ^an aromatic ring directly bonded . The liquid crystal alignment agent according to the above aspect of the invention, wherein the ratio of the compound represented by the formula (1) in the amine compound (B) is 10 mol% or more. The liquid crystal alignment agent according to claim 1 or 2, wherein the compound (A) is selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide. At least one of the groups. The liquid crystal alignment agent according to claim 1 or 2, wherein the compound (A) is a tetracarboxylic dianhydride, and As the tetracarboxylic dianhydride, comprising 2:3,5:6-dianhydride, 2,3,5,6-tetracarboxylic acid selected from bicyclo[2.2.1]heptane, 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, bicyclo[3.3.0]octane-2,4,6 At least one of a group consisting of 8:4,6:8-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride . The liquid crystal alignment agent according to claim 1 or 2, wherein the R ¹ is a divalent hydrocarbon group or a carbon-carbon bond in the divalent hydrocarbon group and adjacent to the Z ¹ a divalent group obtained by introducing -O-, -COO-, -CO-, -NHCO-, -S- or -NH- at at least any position of the position adjacent to the Z ² or having a hetero group a divalent group of the ring; and may have a substituent. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 5. A liquid crystal display element comprising: the liquid crystal alignment film according to claim 6 of the patent application. A retardation film comprising: the liquid crystal alignment film according to claim 6 of the patent application. A method for producing a retardation film, comprising: a step of applying a liquid crystal alignment agent according to any one of claims 1 to 5 to a substrate to form a coating film; a step of irradiating the coating film with light; and a step of applying a polymerizable liquid crystal on the coating film after the light irradiation to harden it. A polymer obtained by using a compound (A) and an amine compound (B) selected from the group consisting of a polyvalent carboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid halide, and a polycarboxylic acid. At least one of a group consisting of a partial esterified product and a hydrazine halide of the partial esterified product, the amine compound (B) comprising a compound represented by the following formula (1): Z ¹ -R ¹ -Z ² (1) In the formula (1), R ¹ is a divalent organic group; and Z ¹ is a nitrogen atom having a ring number of 5 to 7 having a "-NH-" between carbon-carbon bonds in the ring skeleton of the aliphatic ring. a heterocyclic group, a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted; Z ² is a first-order amine group, -NHR ² , or a carbon-carbon bond in a ring skeleton of an aliphatic ring a nitrogen-containing heterocyclic group having a ring number of 5 to 7 having "-NH-", a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted, and R ² is a carbon number of 1 to 15 a monovalent hydrocarbon group in which the aromatic ring is not directly bonded to a nitrogen atom in the case where R ² has an aromatic ring; wherein, in the case where Z ² is "-NHR ² ", Z ² does not have aroma with R ¹ The ring is directly bonded. A compound represented by the following formula (1): Z ¹ -R ¹ -Z ² (1) In the formula (1), R ¹ is a divalent organic group; and Z ¹ is a carbon in a ring skeleton of an aliphatic ring a nitrogen-containing heterocyclic group having a ring number of 5 to 7 having "-NH-" between carbon bonds, a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted; Z ² is a first-order amine a group or -NHR ² , R ² is a monovalent hydrocarbon group having 1 to 15 carbon atoms, and in the case where R ² has an aromatic ring, the aromatic ring is not directly bonded to a nitrogen atom; wherein Z ² is "-NHR ² In the case of Z ² , Z ^{2 is} not directly bonded to the aromatic ring of R ¹ .