TW201634675A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, phase retardation film and method for manufacturing the same, polymer and diamine - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a phase retardation film and a method for manufacturing the same, a polymer, and a diamine, in which the liquid crystal display element, which has high reliability and little uneven distribution in the surrounding area of a sealant, can be obtained from the liquid crystal alignment agent. The present invention also makes it possible for the liquid crystal alighment agent to contain a compound (A) having a partial structure represented by the following formula (1). (In the formula (1), R 1 is a protecting group for protection of amino groups, and two "* 1" represent a bond bonded to a hydrocarbon group).

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, and its production method, polymer and diamine

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

The liquid crystal display element is classified into a plurality of modes depending on the initial alignment state of the liquid crystal molecules in the liquid crystal layer, or the operation when a voltage is applied, and the like, for example, a twisted nematic (TN) type or a super twisted nematic (Super Twisted) is known. Various liquid crystal display elements such as Nematic, 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. From the viewpoint of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal, the material of the liquid crystal alignment film is usually polyimine or a precursor thereof.

In recent years, large-screen and high-definition LCD TVs have become the mainstay, and the popularity of small-sized display terminals such as smart phones or tablet PCs has been increasing, and the demand for high-definition LCD screens has been continuously improved. In this context, various liquid crystal alignment agents have been proposed in order to improve the display quality or reliability of a liquid crystal panel (see, for example, Patent Document 1). Patent Document 1 discloses that a liquid crystal alignment agent contains polyacrylic acid or polyimine which is a group of "-NHA (where A is a tertiary butyl group) by using a polyaminic acid or a polyimine. Obtained as an aromatic diamine of oxycarbonyl).

Further, various optical materials are used for the liquid crystal display device, and the retardation film is used for the purpose of eliminating the coloration of the display or eliminating the dependency of the viewing color and the contrast depending on the visual direction. With respect to the retardation film, a retardation film having the following members: a liquid crystal alignment film formed on the surface of a substrate such as a triacetyl cellulose (TAC) film, and a surface on the liquid crystal alignment film are known. A liquid crystal layer formed by curing a polymerizable liquid crystal. Further, in recent years, in the production of a liquid crystal alignment film in a retardation film, a photo-alignment method is applied to irradiate a polarized or non-polarized radiation to a radiation-sensitive organic thin film formed on a surface of a substrate to impart liquid crystal alignment. A liquid crystal alignment agent for various retardation films for producing a liquid crystal alignment film by this method has been proposed (for example, see Patent Document 2). [Prior Art Literature]

[Patent Document 1] [Patent Document 1] International Publication No. 2013/115228 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-37868

[Problems to be solved by the invention]

The liquid crystal display is manufactured by arranging a pair of substrates on which a liquid crystal alignment film is formed, and arranging liquid crystal between the pair of substrates arranged in the opposing direction. In this case, the pair of substrates are bonded together with a sealing agent such as an epoxy resin. . Here, in the touch screen display screen represented by the smart phone or the tablet PC, in order to make the movable area of the touch screen wider and the miniaturization of the liquid crystal screen, an attempt is made to achieve narrow marginalization. Along with the narrow edge of such a liquid crystal screen, display unevenness caused by a decrease in performance of the liquid crystal alignment film may be observed around the sealant for displaying the screen. In order to achieve high definition of a liquid crystal display, it is required to form a liquid crystal alignment film in which display unevenness (high frame unevenness) is hard to be seen around the sealant.

In addition, with the recent high definition of liquid crystal screens, the demand for display quality has become increasingly strict, and liquid crystal display elements are expected to have high reliability. Further, when a retardation film is produced using a liquid crystal alignment agent, it is required to withstand long-term use (adhesion reliability) with respect to adhesion to a substrate.

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent which can obtain a liquid crystal display element which exhibits high reliability and which exhibits unevenness in display around a sealant. Further, another object of the present invention is to provide a liquid crystal alignment agent which can obtain a retardation film having good adhesion reliability. [Technical means to solve the problem]

The inventors of the present invention have diligently studied in order to solve the problems of the prior art as described above, and found that according to a liquid crystal alignment agent containing a compound having a specific structure, it is possible to obtain both high reliability and display of the periphery of the sealant. The present invention is completed by uniformly reducing the liquid crystal display elements. Specifically, according to the present invention, the following liquid crystal alignment agent, liquid crystal alignment film, and method for producing the same, a liquid crystal display element, a retardation film, a method for producing the same, a polymer, and a compound are provided.

The present invention provides, as one embodiment, a liquid crystal alignment agent containing a compound (A) having a partial structure represented by the following formula (1). [Chemical 1] (In the formula (1), R ¹ is a protecting group of an amine group. Two "*1" represent a bonding bond bonded to a hydrocarbon group)

The present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent as another embodiment. Further, the present invention provides a method for producing a liquid crystal alignment film as another embodiment, the method for producing a liquid crystal alignment film comprising the steps of: applying the liquid crystal alignment agent onto a substrate to form a coating film; The film is irradiated with light to impart alignment ability to the liquid crystal.

The present invention provides a liquid crystal display element including the liquid crystal alignment film as another embodiment. Further, the present invention provides a retardation film comprising the liquid crystal alignment film. Further, the present invention provides a method for producing a retardation film, comprising the steps of: applying the liquid crystal alignment agent onto a substrate to form a coating film; irradiating the coating film with light; and irradiating the light The polymer film is coated on the subsequent coating film and cured.

The present invention provides a polymer as another embodiment, the polymer being at least one polymer selected from the group consisting of a polyimide precursor and a polyimine, and the polymer will have A diamine containing a nitrogen-containing heterocyclic structure having a partial structure represented by the above formula (1) in the ring skeleton is obtained by using it in the reaction. Further, the present invention provides a diamine having a nitrogen-containing heterocyclic ring structure containing a partial structure represented by the above formula (1) in a ring skeleton, as another embodiment. [Effects of the Invention]

According to the liquid crystal alignment agent containing the compound (A), a liquid crystal display element which exhibits high reliability and exhibits unevenness in display around the sealant can be obtained. Further, a retardation film having good adhesion reliability can be obtained.

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

<Compound (A)> The liquid crystal alignment agent of the present invention contains the compound (A) having a partial structure represented by the following formula (1). [Chemical 2] (In the formula (1), R ¹ is a protecting group of an amine group. Two "*1" represent a bonding bond bonded to a hydrocarbon group)

R ¹ in the formula (1) is not particularly limited as long as it functions as a protective group for the amine group, and examples thereof include one obtained by at least one of heat, light, acid, and alkali. Price organic basis. R ¹ preferably is at least by heat from a monovalent organic group, specific examples thereof include for example: a urethane-based protective group, acyl amine protecting group, acyl imine protecting group, sulfonylureas An amine-based protecting group, a group represented by each of the following formulas (1-1) to (1-5), and the like. [Chemical 3] (In the formulae (1-1) to (1-5), Ar ¹ represents a monovalent aromatic ring group having 6 to 10 carbon atoms, R ¹¹ is an alkyl group having 1 to 12 carbon atoms, and R ¹² is a monovalent organic group. "*" indicates the bond of the bond to the nitrogen atom)

Ar ¹ of the formula (1-2) is a group obtained by removing one hydrogen atom from an aromatic ring having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the alkyl group having 1 to 12 carbon atoms of R ¹¹ in the formula (1-4) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. These groups may be linear or may be used. It is branched. Examples of the monovalent organic group of R ¹² include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Among these groups, R ^{12 is} preferably an aryl group having 6 to 10 carbon atoms, more preferably an aromatic ring group such as a phenyl group or a naphthyl group.

Among them, R ^{1 is} preferably from the viewpoint of high desorption from heat or a compound which is derived from R ¹ which is desorbed by heating at the time of film formation, and is discharged as a gas to the outside of the film. A urethane-based protecting group. Specific examples thereof include a third butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethoxycarbonyl group, and a 1,1-dimethyl-2-cyanoethoxy group. Alkylcarbonyl, 9-fluorenylmethoxycarbonyl, allyloxycarbonyl, 2-(trimethyldecyl)ethoxycarbonyl, and the like. Among them, a third butoxycarbonyl group (BOC group) is preferred.

The hydrocarbon group bonded to the bond "*1" in the formula (1) may be any of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The chain hydrocarbon group is preferred, and specific examples thereof include a methylene group, an exoethyl group, and a propyl group. In the case where the hydrocarbon group to which "*1" is bonded is a chain hydrocarbon group, the hydrocarbon group may constitute at least a part of the chain structure or may constitute a part of the cyclic structure. In particular, the compound (A) preferably has a compound represented by the formula (1) in the ring skeleton from the viewpoint of the reliability of the liquid crystal display element and the effect of suppressing the display unevenness in the periphery of the sealant. A compound of a partially structured nitrogen-containing heterocyclic structure (hereinafter also referred to as "specific heterocyclic structure").

Examples of the ring skeleton of a specific heterocyclic structure include a piperidine ring, a piperazine ring, a pyrrolidine ring, a hexamethyleneimine ring, a heptamethyleneimine ring, a homopiperazine ring, and a decahydroquinoline ring. , morpholine ring, 1,2,3,4-tetrahydroquinoline ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, anthracene ring, benzimidazole ring, anthracene ring, indazole ring and the like. Among them, the ring skeleton of the specific heterocyclic structure is preferably a piperidine ring, a piperazine ring, a pyrrolidine ring or a hexamethyleneimine ring. These rings may also have a substituent. Examples of the substituent include a methyl group or an ethyl group.

Specific examples of the specific heterocyclic ring structure include an n-valent group obtained by removing n hydrogen atoms from the structures represented by the following formulas (2-1) to (2-4). In addition, the number of the specific heterocyclic structures which the compound (A) has is not particularly limited, and may be one or plural. Further, the compound (A) may have only one specific heterocyclic structure, or may have two or more specific heterocyclic structures. [Chemical 4]

The embodiment in which the compound (A) is contained in the liquid crystal alignment agent is not particularly limited. For example, the compound (A) may be at least a part of the polymer component in the liquid crystal alignment agent, or may be at least a part of the additive component additionally formulated irrespective of the polymer component in the liquid crystal alignment agent.

- In the case where the compound (A) is a polymer, in the case where the compound (A) is a polymer having a partial structure represented by the formula (1) (hereinafter also referred to as "polymer (A)"), the polymer The main skeleton of (A) is not particularly limited, and examples thereof include a polyimine precursor, a polyimine, a polyoxyalkylene, a polyester, a polyamide, a cellulose derivative, a polyacetal, and a poly A main skeleton such as a styrene derivative, a poly(styrene-phenylmaleimide) derivative, or a poly(meth)acrylate. Further, (meth) acrylate means acrylate and methacrylate. The polyimine precursor may be exemplified by polyamine and polyphthalamide. The polymer (A) may be used alone or in combination of two or more. Among these polymers, the polymer (A) is preferably selected from the group consisting of a polyimide precursor, a polyphthalate, a polyimine, a polyamine, a polyorganosiloxane, and a poly(meth)acrylic acid. At least one of the group consisting of an ester and a polyester is more preferably at least one polymer selected from the group consisting of a polyimide precursor and a polyimine.

The polymer (A) may have a partial structure represented by the formula (1) in any one of a main chain and a side chain of the polymer. Here, the "main chain" of the polymer in the present specification means a "backbone" portion containing the longest atomic chain in the polymer. In addition, the "backbone" portion is allowed to contain a ring structure. Therefore, the phrase "having a partial structure represented by the above formula (1) in the main chain" means that the structure constitutes a part of the main chain. By "side chain" of a polymer is meant the portion that branches from the "backbone" of the polymer.

[Polyuric Acid] The polyamic acid as the polymer (A) can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. The polyamic acid can be obtained by polymerization in which a tetracarboxylic dianhydride having a partial structure represented by the above formula (1) is contained in a monomer composition, and having the formula (1) At least one of the partially structured diamines represented. From the viewpoint of high degree of freedom in the selection of the compound, it is preferred to use a diamine having the partial structure represented by the above formula (1) (hereinafter also referred to as "specific diamine").

(Tetracarboxylic dianhydride) The tetracarboxylic dianhydride used for the synthesis of polyphthalic acid may, for example, be an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic butane tetracarboxylic dianhydride, and the like; and alicyclic tetracarboxylic dianhydride; for example, 1, 2, and 3, 4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-3a, 4,5,9b - tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-8-methyl-3a, 4,5,9b - tetrahydronaphtho[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-di-oxotetrahydro-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-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentane tetracarboxylic dianhydride, ethylene glycol bis(trimellitic anhydride), 1,3-propanediol bis ( Trimellitic anhydride)

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride; in addition, Japanese Patent Special Open 2010 can be used. The tetracarboxylic dianhydride described in JP-A-97188. Further, the tetracarboxylic dianhydride used for the synthesis of the polyamic acid may be used alone or in combination of two or more kinds of these tetracarboxylic dianhydrides.

Among them, the tetracarboxylic dianhydride preferably contains a compound selected from the group consisting of bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-3a, 4,5, 9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-8-methyl-3a, 4,5, 9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8- At least one compound of the group consisting of dianhydride, cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride. The amount of these preferred compounds (the total amount used in the case of using two or more kinds) is preferably set to 5 mol% or more based on the total amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid. More preferably, it is set to 10 mol% or more, and further preferably set to 20 mol% or more.

(Diamine) The specific structure of the specific diamine is not particularly limited as long as it has a partial structure represented by the above formula (1), and preferred examples thereof include the following formula (3-1) to formula (3). -4) Compounds and the like represented by each. [Chemical 5] (In the formulae (3-1) and (3-2), R ² is a monovalent group obtained by removing one hydrogen atom from the ring portion of the specific heterocyclic structure, and X ¹ and X ² are each a single bond or two a valent linking group, X ³ is a trivalent linking group. In the formula (3-3), R ³ is a divalent group obtained by removing two hydrogen atoms from a ring portion of a specific heterocyclic ring structure, and X ⁵ and X ⁶ are respectively independently linking group of formula (3-4) is a single bond or a divalent, X ⁷ and X ⁸ are each independently a single bond or a divalent linking group, R ¹ is a protecting group of an amine, R ⁵ and R ⁶ Each is independently a divalent hydrocarbon group. n is an integer from 1 to 4)

In the formula (3-1) to the formula (3-4), examples of the divalent linking group of X ¹ , X ² , X ⁵ , X ⁶ , X ⁷ and X ⁸ include: -O-, -S. -, -CO-, -COO-, -COS-, -NR ⁴ -, -CONR ⁴ -, -CO-NR ⁴ -CO- (wherein R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein at least one methylene group of the hydrocarbon group is via -O-, -S-, -CO-, -COO-, -COS-, -NR ⁵ -, -CONR ⁵ -, -CO-NR ⁵ -CO- (wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) or the like. In the divalent linking group, the hydrogen atom of the hydrocarbon group may be further substituted with, for example, a halogen atom or the like.

Here, the term "hydrocarbon group" as used herein means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a linear hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and which are composed only of a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group having a structure containing only an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. Among them, it is not necessary to be composed only of the structure of the alicyclic hydrocarbon, and also includes a group having a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. Among them, 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 case where X ¹ , X ² , X ⁵ , X ⁶ , X ⁷ and X ⁸ are divalent hydrocarbon groups, and the chain hydrocarbon group may, for example, be a methylene group, an exoethyl group, a propane diyl group or a butane. An alkanediyl group such as a diyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group or a decanediyl group; a vinyl group, a propylene diyl group, a butylene diyl group, An olefin diyl group such as a pentene diyl group or a hexene diyl group, and these groups may be linear or branched. Further, examples of the alicyclic hydrocarbon group include a cyclohexylene group and the like; and examples of the aromatic hydrocarbon group include a stretched phenyl group, a stretched biphenyl group, and an extended naphthyl group.

Examples of the trivalent linking group of X ³ include a nitrogen atom and a trivalent hydrocarbon group having 1 to 3 carbon atoms. Preferable examples of R ² include a group obtained by removing one hydrogen atom from the ring portion of the structure represented by each of the formulae (2-1) to (2-4). Specific examples of preferred R ³ include, for example: removing two hydrogen atoms obtained from the other groups represented by each ring portion of said structural formula (2-1) to formula (2-4). Further, in the case of R ³ , the two hydrogen atoms removed may be hydrogen atoms bonded to the same atom, or may be hydrogen atoms bonded to different atoms, respectively. The divalent hydrocarbon group of R ⁵ and R ⁶ in the formula (3-4) is preferably a chain hydrocarbon group, and examples thereof include a methylene group, an exoethyl group, and a propyl group. R amino protecting group R ¹ may be applied to the formula (1) described in ^1.

The bonding position of the primary amine group in the formula (3-1) to the formula (3-4) is not particularly limited. For example, in the case of the formula (3-1), the two amine groups of the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to the other groups. In the case of the formula (3-2) to the formula (3-4), an amine group of the aminophenyl group is preferably at the 3 or 4 position with respect to the other group, and more preferably at 4 Bit.

Specific examples of the specific diamine, the compound represented by the formula (3-1), for example, a compound represented by the following formula (X-1) and formula (X-2); 3-2) The compound represented by the following formula (X-3), for example, and the compound represented by the formula (3-3), for example, the following formula (X-4) The compound represented by the formula (3-4), for example, a compound represented by the following formula (Y-1) to formula (Y-8), and the like. Further, the specific diamines may be used alone or in combination of two or more. [Chemical 6] [Chemistry 7]

A specific diamine can be synthesized by appropriately combining a common method of organic chemistry. An example of the method is to synthesize a dinitro intermediate containing a nitro group in place of the primary amine group of the diamine having the partial structure represented by the formula (1), and then using the appropriate reduction system to obtain the obtained dinitrogen A method of amination of a nitro group of a base intermediate.

The method of synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. For example, a method of reacting a hydroxyl group-containing compound having a partial structure represented by the above formula (1) with a halogenated dinitrobenzene in an organic solvent, if necessary, in the presence of a catalyst; The amine group-containing compound having the partial structure represented by the above formula (1) and the halogenated dinitrobenzene are preferably those which are allowed to react in the presence of a catalyst in an organic solvent as needed. The reduction reaction of the dinitro intermediate is preferably carried out using an organic solvent such as 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. However, the order of synthesis of a particular diamine is not limited to the method.

The diamine used for the synthesis of the polyamic acid as the polymer (A) may be only a specific diamine, and other diamines other than the specific diamine may be used in combination.

Examples of the other diamine include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organic decane. Specific examples of such a diamine include aliphatic methylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, and hexamethylene diamine. 1,3-bis(aminomethyl)cyclohexane or the like; examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine) )Wait;

Examples of the aromatic diamine include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, hexadecyloxydiaminobenzene, and ten Octaoxydiaminobenzene, cholestyloxydiaminobenzene, cholesteneoxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate , linoleyl diaminobenzoic acid, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-( (aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, N-(2,4-diaminophenyl)-4-(4-heptylcyclohexyl a diamine containing an alignment group such as a benzoguanamine or a compound represented by the following formula (E-1), [Chem. 8] (In the formula (E-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, and R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single a bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. wherein a and b are not 0) ;

P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl sulfide, 4-aminobenzene 4- 4'-aminobenzoic acid ester, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,7-bis(4-amine Phenoxy) heptane, bis[2-(4-aminophenyl)ethyl]adipate, N,N-bis(4-aminophenyl)methylamine, 1,5-diamine Naphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 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-phenylene diisopropylidene Diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 2, 4-Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N,N'-bis (4 -aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl) - piperazine, 3,5-diaminobenzoic acid, etc.; diamine Examples of the organic oxirane include 1,3-bis(3-aminopropyl)-tetramethyldioxane and the like; in addition, two of those described in JP-A-2010-97188 can be used. amine.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _d -" in the formula (E-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, *-O-, * -COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). The group "-C _c H _2c+1 " may, for example, be 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 decyl group. Trialkyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc., these groups are preferably linear. The two amine groups of the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the formula (E-1) include a compound represented by the following formula (E-1-1) to formula (E-1-4), and the like. [Chemistry 9] Further, as the other diamine for synthesizing the polyamic acid, one of these compounds may be used alone or two or more kinds thereof may be appropriately selected.

When the liquid crystal alignment agent of the present invention is used for a liquid crystal display device of a TN type, an STN type or a vertical alignment type, it is preferred to introduce a liquid crystal alignment ability to the coating film in the side chain of the polyamic acid. Group (liquid crystal alignment group). Here, the liquid crystal alignment group is a group which imparts liquid crystal alignment to the coating film without depending on light irradiation, and specific examples thereof include an alkyl group having 4 to 20 carbon atoms and a fluorine having 4 to 20 carbon atoms. An alkyl group, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, a group in which a plurality of rings are bonded directly or via a linking group, and the like. The polyamic acid having a liquid crystal alignment group can be obtained, for example, by polymerization of a diamine containing the above-mentioned alignment group in the monomer composition. In the case of using a diamine containing an alignment group, from the viewpoint of exhibiting good liquid crystal alignment, it is preferable to set the amount to 3 mol% or more with respect to all diamines used for the synthesis. More preferably, it is set to 5 mol% to 70 mol%.

From the viewpoint of sufficiently obtaining the reliability of the liquid crystal display element and the improvement effect of the frame unevenness tolerance, the use ratio of the specific diamine is preferably set with respect to the total amount of the diamine for synthesizing the polyamic acid. It is 0.5 mol% or more, more preferably 2 mol% or more, and further preferably 10 mol% or more. Further, the upper limit of the use ratio of the specific diamine is not particularly limited, but is preferably set to 100 mol% or less, more preferably 80 mol% or less, and further preferably set to 70 mol%. the following.

In the case where the liquid crystal alignment ability is imparted to the coating film formed of the liquid crystal alignment agent by the photo-alignment method, a polymer having a photo-alignment structure may be used as at least a part of the polymer (A). Specific examples of the photo-alignment structure may be groups exhibiting photo-alignment properties by photoisomerization, photodimerization, photolysis, and the like. Specifically, for example, an azo group containing an azo compound or a derivative thereof as a basic skeleton, a cinnamic acid group containing cinnamic acid or a derivative thereof as a basic skeleton, and a chalcone containing Or a derivative thereof, the chalcone-containing group as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, or a coumarin or a derivative thereof as a basic skeleton a coumarin-containing group, a cyclobutane-containing structure containing cyclobutane or a derivative thereof as a basic skeleton, a bicyclo ring containing a bicyclo[2.2.2] octene or a derivative thereof as a basic skeleton [2.2.2 The structure of octene and the structure including a partial structure represented by the following formula (4) as a basic skeleton. [化10] (In the formula (4), X ⁷ is a sulfur atom, an oxygen atom or -NH-. "*" represents a bond, respectively, wherein at least one of the two "*" is bonded to the aromatic ring)

The polyaminic acid having a photo-alignment structure can be obtained, for example, by polymerization of at least one of a tetracarboxylic dianhydride having a photo-alignment structure and a diamine having a photo-alignment structure in a raw material. In this case, from the viewpoint of sensitivity to light, the use ratio of the monomer having a photo-alignment structure is preferably set to 20 mol% or more with respect to the total amount of the monomer for synthesizing the polymer. More preferably, it is set to 30% by mole to 80% by mole.

(Synthesis of Polylysine) Polylysine can be obtained by reacting a tetracarboxylic dianhydride and a diamine as described above together with a molecular weight modifier. The ratio of use of the tetracarboxylic dianhydride to the diamine for the synthesis reaction of poly-proline is preferably 1 equivalent to the amine group of the diamine and 0.2 equivalent to 2 equivalents of the tetracarboxylic dianhydride. More preferably, the ratio of the acid anhydride group of the tetracarboxylic dianhydride is from 0.3 equivalents to 1.2 equivalents. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and phenyl isocyanate and isocyanate. a monoisocyanate compound such as an ester. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, more preferably from 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.

The organic solvent used for the reaction may, for example, be an aprotic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon or a hydrocarbon. Among these organic solvents, it is preferred to use one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (the first group of organic solvents), or an organic solvent selected from the first group. One or more of the 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 more preferably 30% by weight or less.

With respect to the particularly preferred organic solvent, it is preferred to be selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl azine. And one or more of a group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or in a range of the ratio A mixture of one or more of these solvents with other organic solvents is used. The amount (x) of the organic solvent to be used is preferably set to be 0.1% by weight to 50% by weight based on the total amount (x+y) of the reaction solution and the total amount (y) of the tetracarboxylic dianhydride and the diamine. the amount.

As described above, a reaction solution obtained by dissolving polylysine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, and the poly-proline acid contained in the reaction solution can be separated and used for preparing a liquid crystal alignment agent, or the separated polyamic acid can also be purified and then prepared. Liquid crystal alignment agent. In the case of polycondensation of polylysine to form a polyimine, the reaction solution may be directly supplied to a dehydration ring-closure reaction, or the poly-proline contained in the reaction solution may be separated for dehydration. The ring closure reaction, or the isolated polyamic acid can also be purified for dehydration ring closure reaction. The separation and purification of polylysine can be carried out in accordance with well-known methods.

[Polyurethane] The polyphthalate as the polymer (A) can be obtained, for example, by the following method: [I] reacting the polylysine obtained by the synthesis reaction with an esterifying agent Process; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like. In the present specification, the term "tetracarboxylic acid diester" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the other two are carboxyl groups. The "tetracarboxylic acid diester dihalide" means a compound obtained by esterifying two of the four carboxyl groups of the tetracarboxylic acid and halogenating the other two.

The esterifying agent used in the method [I] may, for example, be a hydroxyl group-containing compound, an acetal compound, a halide or an epoxy group-containing compound. Specific examples of the compound include a hydroxyl group-containing compound such as methanol, ethanol, or propanol, a phenol such as phenol or cresol, and the like, and an acetal compound such as N,N-dimethyl group. Methionine diethyl acetal, N, N-diethylformamide diethyl acetal, etc.; halides include, for example, methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride And 1,1,1-trifluoro-2-iodoethane, etc., and the epoxy group-containing compound is exemplified by propylene oxide.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid by using an alcohol such as methanol or ethanol. Further, the tetracarboxylic acid derivative used in the method [II] may be only a tetracarboxylic acid diester, or a tetracarboxylic dianhydride may be used in combination. As the diamine, a specific diamine exemplified in the synthesis of polylysine may be used alone, or may be used in combination with other diamines.

The reaction of the method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. The organic solvent is exemplified as an organic solvent used for synthesizing an organic solvent of polyamic acid. The dehydration catalyst may, for example, be a halogenated 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium, a carbonylimidazole or a phosphorus-based condensing agent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, more preferably from 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting a tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as sulfinium chloride. Further, the tetracarboxylic acid derivative used in the method [III] may be only a tetracarboxylic acid diester dihalide, or a tetracarboxylic dianhydride may be used in combination. As the diamine, a specific diamine exemplified in the synthesis of polylysine may be used alone, or may be used in combination with other diamines.

The reaction of the method [III] is preferably carried out in an organic solvent in the presence of a suitable base. The organic solvent is exemplified as an organic solvent used for synthesizing an organic solvent of polyamic acid. As the base, for example, a tertiary amine such as pyridine or triethylamine; an alkali metal such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium or potassium can be preferably used. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, more preferably from 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

The polyphthalate contained in the liquid crystal alignment agent may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist. In addition, the reaction solution obtained by dissolving the polyamidate may be directly used for preparing the liquid crystal alignment agent, or the polyphthalate contained in the reaction solution may be separated and then used for preparing the liquid crystal alignment agent, or may be The isolated polyphthalate is purified and used to prepare a liquid crystal alignment agent. The separation and purification of the polyamidite can be carried out in accordance with well-known methods.

[Polyimide] The polyimine which is the polymer (A) can be obtained, for example, by dehydrating and ring-closing a poly-proline which is synthesized as described above.

The polyimine may be a fully ruthenium imide formed by dehydration and ring closure of the proline structure of the polyamic acid as a precursor thereof, or may be a dehydration ring closure of only a part of the structure of the proline. A partial quinone imide of an amine acid structure coexisting with a quinone ring structure. The polyimine used for the reaction preferably has a ruthenium amination ratio of 20% or more, more preferably 30% to 99%, still more preferably 40% to 99%. The ruthenium iodization ratio is a ratio of the number of quinone imine ring structures of the polyimine to the total number of guanine structures and the number of quinone ring structures. Here, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine; or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. , the method of heating as needed. In the method of adding a dehydrating agent and a dehydration ring-closing 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 to be used is preferably from 0.01 mol to 20 mol based on 1 mol of the proline structure of the polyglycolic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. The amount of the dehydration ring-closing catalyst to be 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 for the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as an organic solvent for synthesizing polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing polyimine can be obtained in this manner. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution, or can be used for preparing a liquid crystal alignment agent after separating the polyfluorene imine, or The isolated polyimine can also be purified and used to prepare a liquid crystal alignment agent. These purification operations can be carried out in accordance with well-known methods. In addition to this, polyimine can also be obtained by hydrazylation of polyphthalate.

The polyimine precursor and the polyimine obtained as described above preferably have a solution viscosity of 20 mPa·s to 1,800 mPa·s when formed into a solution having a concentration of 15% by weight, more preferably It has a solution viscosity of 50 mPa·s to 1,500 mPa·s. Further, the solution viscosity (mPa·s) of the polymer is a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer at 25 ° C by an E-type rotational viscometer. The measured value of the prepared 15% by weight polymer solution. The polystyrene-reduced precursor and the polyimine are preferably polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 500,000. Good is 2,000 to 300,000. Further, the molecular weight distribution (Mw/Mn) expressed by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 5 or less, more preferably 3.5 or less. By being in this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

[Polyoxane] The polyoxyalkylene as the polymer (A) can be obtained, for example, by hydrolyzing and condensing a hydrolyzable decane compound. Specific examples thereof include the following methods [1] or [2], and [1] a hydrolyzable decane compound (ms-1) having an epoxy group or the decane compound (ms-1) and other decane compounds. The mixture is hydrolyzed and condensed to synthesize an epoxy group-containing polyoxyalkylene, and then the obtained epoxy group-containing polyoxyalkylene is mixed with a carboxylic acid having a partial structure represented by the formula (1) (hereinafter also referred to as a method of reacting "specific carboxylic acid"); [2] a hydrolyzable decane compound (ms-2) having a partial structure represented by the formula (1), or the decane compound (ms-2) and other decane A method of hydrolytic condensation of a mixture of compounds. Among these methods, the method [1] is simple, and the introduction rate of the partial structure represented by the above formula (1) in the polymer (A) can be improved, which is preferable in this respect.

Specific examples of the decane compound (ms-1) include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl group. Methyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4- Epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, and the like. The decane compound (ms-1) may be used alone or in combination of two or more.

The other decane compound is not particularly limited as long as it is a hydrolyzable decane compound, and examples thereof include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, and phenyl trimethoxy decane. Alkoxydecane such as phenyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane; 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxylate Decane, 3-ureidopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-(3-cyclohexylamino)propyltrimethoxy Nitrogen-sulfur-containing alkoxydecane such as decane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane; 3-(methyl)propenyloxypropyltrimethoxy Decane, 3-(methyl)propenyloxypropyltriethoxydecane, 6-(methyl)propenyloxyhexyltrimethoxydecane, 3-(methyl)propenyloxypropylmethyl Dimethoxy decane, 3-(meth) propylene methoxy propyl methyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, p-styryl trimethoxy decane, etc. Not full The alkoxy decane of the bond and the bond may, for example, be trimethoxydecylpropyl succinic anhydride or the like. Other decane compounds may be used alone or in combination of two or more.

As described above, the hydrolysis/condensation reaction of the decane compound is carried out by reacting one or two or more kinds of decane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. In the method of the above [1], from the viewpoint that the partial structure represented by the formula (1) can be sufficiently introduced into the polymer and the side reaction due to the excess amount of the epoxy group is suppressed, The epoxy group-containing polyoxyalkylene has an epoxy equivalent of preferably from 100 g/mol to 10,000 g/mol, more preferably from 150 g/mol to 1,000 g/mol. Therefore, it is preferred to adjust the use ratio of the decane compound (ms-1) so that the epoxy equivalent of the obtained polyoxyalkylene is in the above range when the epoxy group-containing polyoxyalkylene is synthesized. In the hydrolysis/condensation reaction, the use ratio of water is preferably from 0.5 mol to 100 mol, more preferably from 1 mol to 30 mol, per mol of the decane compound (total amount).

Examples of the catalyst used in the hydrolysis/condensation reaction include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. The amount of the catalyst to be used varies depending on the type of the catalyst, the reaction conditions such as the temperature, and the like, and should be appropriately set. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 moles per mole of the total amount of the decane compound. ~ 1 times Mo. The organic solvent used in the hydrolysis/condensation reaction may, for example, be a hydrocarbon, a ketone, an ester, an ether or an alcohol. Among these organic solvents, it is preferred to use an organic solvent which is not water-soluble or poorly water-soluble. The organic solvent is preferably used in an amount of from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of the total of the decane compound used for the reaction.

The hydrolysis/condensation reaction is preferably carried out, for example, by heating in an oil bath or the like. In the hydrolysis/condensation reaction, it is preferred to set the heating temperature to 130 ° C or lower, and more preferably to 40 ° C to 100 ° C. The heating time is preferably set to 0.5 hours to 12 hours, and more preferably set to 1 hour to 8 hours. The mixture may be stirred during heating or placed under reflux. Further, after the completion of the reaction, it is preferred to wash the organic solvent layer separated and extracted from the reaction liquid by water. In the cleaning, it is preferred to wash the water by washing with a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like). The cleaning is carried out until the water layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed, whereby the target polyoxyalkylene can be obtained. Further, the method for synthesizing the polyoxyalkylene is not limited to the hydrolysis/condensation reaction, and may be carried out, for example, by a method in which a hydrolyzable decane compound is reacted in the presence of oxalic acid and an alcohol.

In the method of [1], the epoxy group-containing polyoxyalkylene obtained by the reaction is subsequently reacted with a specific carboxylic acid. Thereby, the epoxy group of the epoxy group-containing polyoxyalkylene is reacted with a carboxylic acid to obtain a polyoxyalkylene having a partial structure represented by the above formula (1). The specific carboxylic acid is not particularly limited as long as it has a partial structure represented by the above formula (1), and is preferable from the viewpoints of reliability of the liquid crystal display element and suppression of improvement in display unevenness around the sealant. The carboxylic acid having a specific heterocyclic structure, for example, a compound represented by each of the following formulas (A-3) to (A-6), and the like can be given. [11] Further, the specific carboxylic acids may be used alone or in combination of two or more.

In the synthesis of the polyoxyalkylene as the polymer (A), the carboxylic acid used in the reaction with the epoxy group-containing polyoxyalkylene may be only a specific carboxylic acid, or a carboxylic acid other than the specific carboxylic acid may be used in combination. . The other carboxylic acid is not particularly limited as long as it is a carboxylic acid having no partial structure represented by the above formula (1), and examples thereof include a carboxylic acid having the liquid crystal alignment group. Other carboxylic acids may be used alone or in combination of two or more.

The ratio of the carboxylic acid to be reacted with the epoxy group-containing polyoxyalkylene is preferably from 0.001 mol to 1.5 mol, based on 1 mol of the epoxy group of the polyoxyalkylene. Preferably, it is set to 0.01 mol to 1.0 mu. The ratio of use of the specific carboxylic acid to the total amount of the carboxylic acid to be reacted with the epoxy group-containing polyoxyalkylene is preferably set to 5 mol% or more, and more preferably set to 10 mol% or more.

The reaction of the epoxy group-containing polyoxyalkylene with the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst, for example, a compound known as a so-called hardening accelerator for promoting the reaction of an organic base or an epoxy compound can be used. Among them, a tertiary organic amine or a tertiary organic amine is preferred. The use ratio of the catalyst is preferably 100 parts by weight or less, more preferably 0.01 parts by weight to 100 parts by weight, even more preferably 0.1 parts by weight to 20 parts by weight per 100 parts by weight of the epoxy group-containing polyoxyalkylene oxide.

The organic solvent used in the reaction may, for example, be a hydrocarbon, an ether, an ester, a ketone, a decylamine, an alcohol or the like. Among these organic solvents, from the viewpoints of the solubility of the raw materials and products, and the ease of purification of the product, it is preferably at least one selected from the group consisting of ethers, esters and ketones, and a particularly preferable solvent. Specific examples thereof include 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate. The organic solvent is preferably used in a ratio of a solid content concentration (a ratio of a total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, more preferably a solid. The component concentration is used in a ratio of 5 wt% to 50 wt%.

The reaction temperature of the reaction is preferably from 0 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours. Further, after the completion of the reaction, it is preferred to wash the organic solvent layer separated and extracted from the reaction liquid by water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as needed, and then the solvent is removed, whereby the target polyoxyalkylene can be obtained.

The polystyrene-equivalent weight average molecular weight (Mw) measured by polyoxymethane as the polymer (A) by GPC is preferably in the range of 100 to 50,000, more preferably in the range of 200 to 10,000. . When the weight average molecular weight of the polyoxyalkylene is within the above range, it is easy to handle when producing a liquid crystal alignment film, and the obtained liquid crystal alignment film has sufficient material strength and characteristics.

[Poly(meth)acrylate] The poly(meth)acrylate as the polymer (A) can be obtained, for example, by a method in which a (meth)acrylic monomer having an epoxy group (ma-1) is obtained. Or the mixture of the (meth)acrylic monomer (ma-1) and another (meth)acrylic monomer is polymerized in the presence of a polymerization initiator, and the resulting polymer (hereinafter also referred to as " The epoxy group-containing poly(meth)acrylate") is reacted with a specific carboxylic acid.

The (meth)acrylic monomer (ma-1) is, for example, an unsaturated carboxylic acid ester having an epoxy group. Specific examples thereof include glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and (methyl). 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6,7-ring (meth) acrylate Oxyheptyl ester, α-ethyl acrylate 6,7-epoxyheptyl ester, 4-hydroxybutyl glycidyl acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate Wait. Further, the (meth)acrylic monomer (ma-1) may be used alone or in combination of two or more.

Examples of the other (meth)acrylic monomer include unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, and vinylbenzoic acid; Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (A) 2-ethylhexyl acrylate, lauryl (meth)acrylate, trimethoxydecyl propyl (meth)acrylate, methoxyethyl (meth)acrylate, (meth)acrylic acid-N , N-dimethylaminoethyl ester, methoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. An ester; an unsaturated polycarboxylic acid anhydride such as maleic anhydride, itaconic anhydride or cis-1,2,3,4-tetrahydrophthalic anhydride. Further, other (meth)acrylic monomers may be used alone or in combination of two or more kinds.

When the poly(meth) acrylate is synthesized, the total amount (molar number) of the epoxy group per 1 g of the epoxy group-containing poly(meth) acrylate is preferably 5.0 × 10 ^-5 mol/g or more. More preferably, it is 1.0 × 10 ^-4 mol / g ^- 1.0 × 10 ^-2 mol / g, and further preferably 5.0 × 10 ^-4 mol / g ^- 5.0 × 10 ^-3 mol / g. Therefore, the use ratio of the (meth)acrylic monomer (m-1) is preferably such that the total number of moles per 1 g of the epoxy group-containing poly(meth)acrylate epoxy group is as described above. The way the range is adjusted.

Further, other monomers other than the (meth)acrylic monomer may be used in the polymerization. Examples of the other monomer include a conjugated diene compound such as 1,3-butadiene or 2-methyl-1,3-butadiene; and aromatic such as styrene, methyl styrene or divinyl benzene. Group vinyl compounds and the like. The ratio of use of the other monomer is preferably set to 30 mol% or less, and more preferably 20 mol% or less, based on the total of the monomers for synthesizing the poly(meth)acrylate.

The polymerization using a (meth)acrylic monomer is preferably carried out by radical polymerization. The polymerization initiator to be used in the polymerization reaction may, for example, be an initiator which is usually used in radical polymerization, and examples thereof include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis ( Azo compound such as 2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzammonium peroxide, lauric peroxide An organic peroxide such as tributyl butyl peroxyacetate or 1,1'-bis(t-butylperoxy)cyclohexane; hydrogen peroxide; including oxidation of these peroxides and reducing agents Reduced initiators, etc. Among these compounds, an azo compound is preferred, and 2,2'-azobis(isobutyronitrile) is more preferred. The polymerization initiator may be used alone or in combination of two or more kinds of these compounds. The use ratio of the polymerization initiator is preferably from 0.01 part by weight to 50 parts by weight, more preferably from 0.1 part by weight to 40 parts by weight, based on 100 parts by weight of all the monomers used for the reaction.

The polymerization of the (meth)acrylic monomer is preferably carried out in an organic solvent. The organic solvent used in the reaction may, for example, be an alcohol, an ether, a ketone, a guanamine, an ester or a hydrocarbon compound. Among these organic solvents, it is preferred to use at least one selected from the group consisting of alcohols and ethers, and more preferably to use a partial ether of a polyol. Preferable examples thereof include diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate. Further, the organic solvent may be used alone or in combination of two or more kinds of these organic solvents.

In the polymerization reaction of the (meth)acrylic monomer, the reaction temperature is preferably set to 30 ° C to 120 ° C, and more preferably 60 ° C to 110 ° C. The reaction time is preferably set to 1 hour to 36 hours, and more preferably set to 2 hours to 24 hours. Further, the amount (a) of the organic solvent used is preferably set to be 0.1 to 50% by weight based on the total amount (a+b) of the reaction solution and the total amount of the monomers used for the reaction (b). the amount.

For the epoxy group-containing poly(meth) acrylate obtained by the reaction, a specific carboxylic acid is then reacted therewith. A description of the polyoxane can be applied to a particular carboxylic acid. Further, in the case of the reaction, a specific carboxylic acid may be used singly or a carboxylic acid other than the specific carboxylic acid may be used in combination. The ratio of use of the carboxylic acid reacted with the epoxy group-containing poly(meth) acrylate is preferably 1 mol based on the total of the epoxy groups contained in the epoxy group-containing poly(meth) acrylate. Set to 0.001 m to 0.95 m. More preferably, it is 0.01 mol to 0.9 mol, and further preferably set to 0.05 mol to 0.8 mol.

The reaction of the epoxy group-containing poly(meth) acrylate with the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. Here, the catalyst to be used for the reaction is, for example, a compound exemplified as a catalyst which can be used in the synthesis of polysiloxane. Among these compounds, a quaternary ammonium salt is preferred. The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 parts by weight to 100 parts by weight, even more preferably 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the epoxy group-containing poly(meth) acrylate. Parts by weight.

The organic solvent used in the reaction can be exemplified by an organic solvent which can be used in the polymerization of a (meth)acrylic monomer, and among them, an ester is preferred. The organic solvent is preferably used in a ratio of a solid content concentration (a ratio of a total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, more preferably a solid. The component concentration is used in a ratio of 5 wt% to 50 wt%. The reaction temperature is preferably set to 0 ° C to 200 ° C, and more preferably set to 50 ° C to 150 ° C. The reaction time is preferably set to 0.1 to 50 hours, more preferably 0.5 to 20 hours.

A solution containing the poly(meth) acrylate as the polymer (A) can be obtained in this manner. The reaction solution may be directly used for preparing a liquid crystal alignment agent, or may be used for preparing a liquid crystal alignment agent after separating the poly(meth)acrylate contained in the reaction solution, or may also separate the separated poly(meth)acrylic acid. After the ester is purified, it is used to prepare a liquid crystal alignment agent. The separation and purification of the poly(meth) acrylate can be carried out in accordance with a well-known method. Further, the method for synthesizing the poly(meth)acrylate as the polymer (A) is not limited to the above method. For example, it can also be obtained by subjecting a (meth)acrylic monomer having a partial structure represented by the formula (1) or the (meth)acrylic monomer to other (meth)acrylic acid. A method in which a mixture of monomers is polymerized in the presence of a polymerization initiator or the like.

From the viewpoint of ensuring the liquid crystal alignment property of the liquid crystal alignment film to be formed and ensuring the temporal stability of the liquid crystal alignment property, the polystyrene-equivalent number average molecular weight measured by GPC on the poly(meth)acrylate (Mn) is preferably from 250 to 500,000, more preferably from 500 to 100,000, still more preferably from 1,000 to 50,000.

[Polyester] The polyester as the polymer (A) can be obtained, for example, by reacting a dicarboxylic acid having a partial structure represented by the above formula (1) with a diepoxy compound. Here, the diepoxide compound is, for example, in addition to ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexyl In addition to the diol diglycidyl ether, a diepoxy compound described in JP-A-2013-113937 can be mentioned. The ratio of use of the diepoxy compound to the dicarboxylic acid compound used in the synthesis reaction of the polyester is preferably 0.2 equivalent to 2 based on 1 equivalent of the carboxyl group contained in the dicarboxylic acid compound. The equivalent weight is more preferably from 0.3 equivalent to 1.2 equivalents.

The reaction of the dicarboxylic acid with the diepoxy compound is preferably carried out in the presence of an organic solvent. Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and N,N-dimethylimidazolidine. An aprotic polar solvent such as ketone, dimethyl hydrazine, γ-butyrolactone, tetramethylurea or hexamethylphosphonium triamine; phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol . The reaction temperature is preferably from 0 ° C to 250 ° C, more preferably from 50 ° C to 180 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 2 to 12 hours.

A solution containing the polyester as the polymer (A) can be obtained in this manner. The reaction solution may be directly supplied to prepare a liquid crystal alignment agent, or the polyester contained in the reaction solution may be separated and supplied to prepare a liquid crystal alignment agent, or the separated polyester may be purified and then supplied to prepare a liquid crystal alignment agent. The separation and purification of the polyester can be carried out in accordance with a well-known method.

The polyester obtained as described above preferably has a solution viscosity of 20 mPa·s to 1,800 mPa·s when it is made into a solution having a concentration of 15% by weight, more preferably 50 mPa·s to 1,500 mPa. · s solution viscosity. In addition, the solution viscosity (mPa·s) of the polyester is a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer at 25 ° C by an E-type rotational viscometer. A value obtained by measuring a 15% by weight polymer solution prepared. In addition, from the viewpoint of ensuring the liquid crystal alignment property of the liquid crystal alignment film to be formed and ensuring the temporal stability of the liquid crystal alignment property, the polystyrene-equivalent number average molecular weight (Mn) measured by GPC on the polyester. It is preferably from 250 to 500,000, more preferably from 500 to 100,000, still more preferably from 1,000 to 50,000.

When the compound (A) is an additive, the compound (A) (hereinafter also referred to as "low molecular compound (A)")) as an additive preferably has a molecular weight of 1,000 or less. More preferably, the low molecular weight compound (A) has a molecular weight of 800 or less, more preferably 700 or less, and particularly preferably 500 or less. In addition, the molecular weight of the low molecular compound (A) is preferably 100 or more, and more preferably 150 or more, from the viewpoint of suppressing volatilization of the compound (A) at the time of post-baking. When the low molecular weight compound (A) has a partial structure represented by the above formula (1), the remaining structure is not particularly limited, and the reliability of the liquid crystal display element and the effect of suppressing display unevenness in the periphery of the sealant are high. From the standpoint, preferred are compounds having a specific heterocyclic structure. The low molecular compound (A) may have only a partial structure represented by the above formula (1), or may have a plurality of partial structures represented by the above formula (1). Preferably one to four.

The low molecular compound (A) preferably has a partial structure represented by the above formula (1) and has a functional group which interacts with a functional group possessed by a polymer component in the liquid crystal alignment agent (hereinafter also referred to as " Specific functional group"). The term "interaction" as used herein refers to the formation of covalent bonds between molecules or the formation of weaker molecular forces than covalent bonds (eg, ion-dipole interactions, dipole-dipole interactions, hydrogen bonds, van der Waals). Forces such as electromagnetic forces acting between molecules). By having such a functional group, the effect of suppressing the elution of the low molecular compound (A) from the liquid crystal alignment film is improved, and the introduction effect of the partial structure represented by the above formula (1) can be sufficiently obtained, and from this viewpoint, it is preferable. .

The specific functional group can be appropriately selected depending on the functional group which the polymer component has. For example, in the case of a liquid crystal alignment agent containing a polyimine or a precursor thereof as a polymer component, the specific functional group is preferably a functional group that interacts with a carboxyl group or a quinone imine group, specifically, for example, An epoxy group, an amine group, a carboxyl group, an alkoxyalkyl group, etc. are mentioned. The number of the specific functional groups which the low molecular compound (A) has is preferably one or more, more preferably one to four.

Specific examples of the low molecular compound (A) include a compound represented by the following formula (A-1) and formula (A-2), and each of the formula (A-3) to formula (A-6). The compound shown and the like. [化12] Further, the low molecular compound (A) may be used alone or in combination of two or more.

The compounding ratio of the compound (A) is preferably appropriately selected depending on whether the compound (A) is a polymer or an additive. For example, the blending ratio of the polymer (A) is preferably set to 5 parts by weight or more, and more preferably 10 parts by weight or more, based on 100 parts by weight of the total of the polymer components contained in the liquid crystal alignment agent. It is preferably set to 30 parts by weight or more. When the ratio is less than 5 parts by weight, unevenness in the periphery of the sealant tends to occur, and the reliability of the obtained liquid crystal display element tends to be inferior. In addition, the blending ratio of the low molecular weight compound (A) is preferably set to 0.05 parts by weight or more, more preferably 0.1 part by weight or more, and further preferably set to 100 parts by weight based on the total of the polymer components. It is 0.2 parts by weight or more. In addition, the upper limit of the compounding ratio of the low molecular compound (A) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and further preferably 30 parts by weight based on the total of the polymer components. It is set to 20 parts by weight or less. When the content ratio of the low molecular weight compound (A) is less than 0.05 parts by weight, it is difficult to obtain an effect of reducing unevenness in the periphery of the sealant or an effect of improving afterimage characteristics, and if it exceeds 50 parts by weight, electrical properties are lowered. The tendency to be poor in reliability.

In addition, by using a liquid crystal alignment agent containing the compound (A) having a partial structure represented by the above formula (1), it is possible to suppress display unevenness around the sealant or to improve the reliability of the liquid crystal display element. It is determined, but as a hypothesis, the protective group (R ¹ ) in the partial structure represented by the formula (1) can be considered to be, for example, heating during post-baking, or light irradiation to the liquid crystal alignment film, or acid or alkali. The detachment was carried out under the condition that the partial structure (secondary amine group) after the detachment exhibited high alkalinity, thereby exhibiting high reliability and excellent frame unevenness tolerance. Further, when the partial structure represented by the above formula (1) is contained in the ring skeleton, it is presumed that one of the reasons is that steric hindrance is larger than that of the non-annular structure, and aggregation is suppressed. Therefore, the reliability and the improvement effect of the frame unevenness tolerance are further improved.

Further, when a compound having a secondary or tertiary amine group such as piperidine or piperazine is introduced into a liquid crystal alignment agent, precipitation of a compound is likely to occur due to high polarity. On the other hand, it is considered that the solubility of the compound in a solvent can be improved by protecting the secondary amine group with R ¹ , and thus it can be applied to a liquid crystal alignment agent. The liquid crystal alignment film obtained by using the liquid crystal alignment agent containing the compound (A) has a high voltage holding ratio (initial VHR) at the start of voltage application, and can be preferably used, for example, in a low-frequency driving type liquid crystal display in recent years. element.

<Other components> When the liquid crystal alignment agent of the present invention contains the compound (A) as an additive component, it contains a polymer component together with the low molecular compound (A) as an additive. As the polymer component, a polymer having a partial structure represented by the formula (1), a polymer having no partial structure represented by the formula (1) (hereinafter referred to as "other polymer"), or a mixture of these polymers.

(Other polymer) The main skeleton of the other polymer is not particularly limited, and examples thereof include a polyimide precursor, a polyimine, a polyoxyalkylene, a polyester, a polyamide, a cellulose derivative, and the like. A main skeleton such as a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, or a poly(meth)acrylate. Among these polymers, preferred is selected from the group consisting of a polyimide precursor, a polyimine, a polyamine, a polyorganosiloxane, a poly(meth)acrylate, and a polyester. At least one, more preferably at least one selected from the group consisting of a polyimide precursor, a polyimine, and a polyoxyalkylene. Further, the other polymers may be used alone or in combination of two or more.

In the case where the liquid crystal alignment agent of the present invention contains the polymer (A), the other polymer may be contained together with the polymer (A) for the purpose of, for example, improving electrical properties or solution properties. The blending ratio of the other polymer in this case is preferably 30 parts by weight or less, more preferably 0.1 parts by weight to 20 parts by weight, based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent. Further preferably, it is set to be 0.3 parts by weight to 10 parts by weight.

In addition, the liquid crystal alignment agent of the present invention may contain other components as needed. Examples of the component include a compound having at least one epoxy group in the molecule, a compound having at least one oxetanyl group in the molecule, a functional decane compound, a metal chelate compound, a curing accelerator, a surfactant, and an anti-antibody. Oxidizing agents, sensitizers, preservatives, etc. The compounding ratio of these components can be appropriately selected depending on various compounds within a range that does not impair the effects of the present invention.

<Solvent> The liquid crystal alignment agent of the present invention is prepared in the form of a liquid composition which is preferably dispersed or dissolved in the compound (A) and other components used as needed. Made in a solvent.

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethyl group. Acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate , ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene 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 Ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These organic solvents may be used alone or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent (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, etc., and is preferably 1 The range of % by weight to 10% by weight. In other words, the liquid crystal alignment agent 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 coatability is lowered. 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 to apply the liquid crystal alignment agent on the substrate. For example, when a liquid crystal alignment agent for a liquid crystal display element is applied onto a substrate by a spinner method, it is particularly preferable that the solid content concentration (the total weight of all components other than the solvent in the liquid crystal alignment agent is in the liquid crystal alignment) The proportion in the total weight of the agent is 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 to 9 wt%, thereby setting the solution viscosity to a range of 12 mPa·s to 50 mPa·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 a range of 3 mPa·s to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 10 ° C to 50 ° C, more preferably from 20 ° C to 30 ° C. In addition, from the viewpoint of the applicability of the liquid crystal alignment agent and the film thickness of the formed coating film, the liquid crystal alignment agent for the retardation film is preferably a solid concentration of the liquid crystal alignment agent of 0.2 weight. The range of % to 10% by weight is more preferably in the range of 3% by weight to 10% by weight.

<Liquid Crystal Display Element and Phase Difference Film> A liquid crystal alignment film can be produced by using the liquid crystal alignment agent described above. Further, the liquid crystal alignment film formed using the liquid crystal alignment agent can be preferably used for 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 will be described.

[Liquid Crystal Display Element] The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element is not particularly limited, and can be applied to various operation modes such as TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, and OCB type.

The liquid crystal display element can be produced, for example, by a method including the following steps (1-1) to (1-3). In the step (1-1), the use of the substrate differs depending on the operation mode required. Step (1-2) and step (1-3) are common to each working mode.

[Step (1-1): Formation of Coating Film] First, a liquid crystal alignment agent is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. (1-1A) In the case of manufacturing a liquid crystal display element such as a TN type, an STN type or a VA type, first, two substrates provided with a patterned transparent conductive film are used as a pair, and each of the transparent conductive films Preferably, the liquid crystal alignment agent is applied to the forming surface by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method. For the substrate, for example, a transparent substrate containing the following materials: glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic ring) can be used. Plastics such as olefins. A transparent conductive film provided on one surface of the substrate may be: a Nesser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and containing indium oxide-tin oxide (In ₂ O ₃ -SnO _{2 )} Indium Tin Oxide (ITO) film or the like. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and a mask having a desired pattern when forming a transparent conductive film may be used. Method, etc. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface on which the coating film is formed on the surface of the substrate 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 carry out preheating (prebaking) for the purpose of preventing dripping of the liquid crystal alignment agent to be applied. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Then, the simmering (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally isocyanating the proline structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably from 80 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed as described above is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

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

In any of the above (1-1A) and (1-1B), after the liquid crystal alignment agent is applied onto the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. In this case, when at least one of polyphthalic acid, polyphthalate, and polyimine is blended in the liquid crystal alignment agent, the coating film may be further heated to form a liquid crystal alignment. The poly-proline, polylysine and polyimine blended in the agent are subjected to a dehydration ring-closing reaction to prepare a further yttrium imidized coating film.

[Step (1-2): Orientation ability imparting treatment] When a TN type, STN type, IPS type or FFS type liquid crystal display element is manufactured, the coating film formed in the above step (1-1) is imparted. Processing of liquid crystal alignment capability. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. The alignment ability imparting treatment may be a rubbing treatment in which a coating film is rubbed in a predetermined direction by a roll wound with a cloth such as nylon, rayon, or cotton, and the polarized or non-polarized radiation of the coating film is irradiated. Processing and so on. On the other hand, in the case of producing a VA liquid crystal display element, the coating film formed in the above step (1-1) can be directly used as a liquid crystal alignment film, and the alignment ability imparting treatment can be performed on the coating film.

In the light alignment treatment, for the radiation to be applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In the case where the radiation is polarized, it may be linearly polarized or partially polarized. Further, in the case where the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction, or these directions may be combined. When the non-polarized radiation is irradiated, the direction of the irradiation is set to the oblique direction. As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light of a preferred wavelength range can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of the radiation is preferably from 100 J/m ² to 50,000 J/m ² , more preferably from 300 J/m ² to 20,000 J/m ² . Further, in order to improve the reactivity, the light irradiation of the coating film can be carried out while heating the coating film. The temperature at the time of heating is usually from 30 ° C to 250 ° C, preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C.

Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment so that the liquid crystal alignment film has different liquid crystal alignment ability depending on the region: a part of the liquid crystal alignment film is irradiated with ultraviolet rays, thereby making a part of the liquid crystal alignment film After the treatment of the pretilt angle change or after forming a resist film on a portion of the surface of the liquid crystal alignment film, rubbing treatment is performed in a direction different from the previous rubbing treatment, and then the resist film is removed. In this case, the field of view characteristics of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a polymer sustained alignment (PSA) type liquid crystal display element.

[Step (1-3): Construction of Liquid Crystal Cell] (1-3A) Two sheets of a substrate on which a liquid crystal alignment film is formed as described above are prepared, and liquid crystal is disposed between two substrates arranged in the opposite direction to produce liquid crystal unit. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a method that has been known for a long time. First, the two substrates are arranged to face each other with a gap (cell gap) so that the respective liquid crystal alignment films face each other. Then, the peripheral portion of the two substrates is bonded together using a sealant, and the filling liquid crystal is injected into the cell gap defined by the surface of the substrate and the sealant, and then the injection hole is sealed, thereby manufacturing a liquid crystal cell. In addition, the second method is a method called a One Drop Fill (ODF) method. On a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, for example, an ultraviolet curable sealant is applied, and liquid crystal is dripped at a predetermined number of places on the liquid crystal alignment film surface. Thereafter, the other substrate is bonded in such a manner that the liquid crystal alignment film faces each other, and the liquid crystal is pushed away from the entire surface of the substrate. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using any of the methods, it is preferable to further heat the liquid crystal cell produced as described above until the liquid crystal used is in the same phase, and then slowly cool to room temperature, thereby removing the liquid crystal filling. Flow alignment.

As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. The liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxy azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester liquid crystal can be used. , a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. Further, for example, the following components may be added to the liquid crystal: cholesteric liquid crystal such as cholesteryl choline, cholesteryl phthalate or cholesteryl carbonate; and the trade name "C-15" or " A chiral agent sold by CB-15" (manufactured by Merck); a ferroelectric liquid crystal such as a nonoxybenzylidene-p-amino-2-methylbutylcinnamate or the like.

(1-3B) In the case of producing a PSA type liquid crystal display device, a liquid crystal cell is constructed in the same manner as in the above (1-3A) except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Then, a voltage is applied between the conductive films of the pair of substrates, and the liquid crystal cells are irradiated with light in this state. The voltage applied here can be set, for example, to a direct current or alternating current of 5 V to 50 V. Further, as the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. As the light source for illuminating light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light of the preferred wavelength range can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably from 1,000 J/m ² to 200,000 J/m ² , more preferably from 1,000 J/m ² to 100,000 J/m ² .

(1-3C) In the case of forming a coating film on a substrate using a liquid crystal alignment agent containing a compound (polymer or additive) having a photopolymerizable group, a method of manufacturing a liquid crystal display element by the following steps can be employed: The liquid crystal cell is constructed in the same manner as in the above (1-3A), and then a voltage is applied between the conductive films of the pair of substrates, and the liquid crystal cell is irradiated with light in this state. According to this method, the advantage of the PSA mode can be achieved with a small amount of light irradiation. The applied voltage can be set, for example, to a direct current or alternating current of 0.1 V to 30 V. Regarding the conditions of the irradiated light, the description of the above (1-3B) can be applied.

Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, whereby a liquid crystal display element can be obtained. The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing plate obtained by sandwiching a polarizing film called "H film" with a cellulose acetate protective film, or a polarizing plate containing the H film itself. The "H film" is formed by stretching the polyvinyl alcohol while absorbing it.

[Retardation Film] Next, a method of producing a retardation film using a liquid crystal alignment agent will be described. When the retardation film is produced, the liquid crystal alignment direction can be arbitrarily formed on the substrate by suppressing the generation of dust or static electricity in the step and forming a uniform liquid crystal alignment film, and by using a suitable mask when irradiating the radiation. In terms of different regions, it is preferred to utilize a photo-alignment method. Specifically, it can be manufactured by the following steps (2-1) to (2-3).

[Step (2-1): Formation of Coating Film Using Liquid Crystal Aligning Agent] First, a liquid crystal alignment agent is applied onto a substrate to form a coating film. The substrate used herein may suitably be exemplified: comprising triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polyamine, polyimine, A transparent substrate of a synthetic resin such as polymethyl methacrylate or polycarbonate. Among these, 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 from the viewpoint 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 to the surface of the substrate and the coating film, a previously known pretreatment can be performed on the surface on which the coating film is formed on the surface of the substrate.

The retardation film is often used in combination with a polarizing film. In this case, in order to exhibit desired optical characteristics, it is necessary to closely control the angle of the polarizing axis of the polarizing film 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 angle of the retardation film while aligning it. The step on the polarizing film. In addition, it is thereby possible to contribute to an 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 preferred to use a liquid crystal alignment agent to manufacture by a photoalignment method.

The coating method of the liquid crystal alignment agent on the substrate can be carried out by a suitable coating method, for example, a roll coater method, a spinner method, a printing method, an inkjet method, a bar coater method, an extrusion die method, or the like. Direct gravure coater method, chamber doctor coater method, offset gravure coater method, single roll conformal coater method, reverse-spinning coater method using small-diameter gravure roll, Three reverse roll coater methods, four reverse roll coater methods, slot die method, air knife coater method, normal roll coater method, blade coater method, Knife coater method, impregnation coater method, MB coater method, MB reverse coater method, and the like. After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably set to 40 ° C to 150 ° C, and more preferably set to 80 ° C to 140 ° C. The heating time is preferably set to 0.1 minute to 15 minutes, and more preferably set to 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, more preferably from 5 nm to 500 nm.

[Step (2-2): Light Irradiation Step] Then, the coating film formed on the substrate as described above is irradiated with light, whereby the liquid crystal alignment ability is imparted to the coating film to form a liquid crystal alignment film. The description of the light alignment process of the above step (1-2) can be applied to the type, wavelength, irradiation direction, and light source of the light to be irradiated. The amount of light to be irradiated is preferably set to 0.1 mJ/cm ² to 1,000 mJ/cm ² , more preferably 1 mJ/cm ² to 500 mJ/cm ² , and further preferably set to 2 mJ/ Cm ² to 200 mJ/cm ² .

[Step (2-3): Formation of Liquid Crystal Layer] Then, the polymerizable liquid crystal is applied onto the coating film after light irradiation as described above and cured. 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 polymerized by at least one of heating and light irradiation. For example, Non-Patent Document 1 ("UV-curable liquid crystal and its application", liquid crystal, Vol. 3, No. 1 (1999), pp34~ can be used as the polymerizable liquid crystal. The nematic liquid crystal described in 42). Further, it may be a twisted nematic alignment type liquid crystal to which a cholesteric liquid crystal, a disk type liquid crystal, or 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 be a composition further containing a well-known polymerization initiator, a suitable solvent, and the like. When a polymerizable liquid crystal as described above is applied onto the formed liquid crystal alignment film, for example, a bar coater method, a roll coater method, a spinner method, a printing method, an inkjet method, or the like can be used. 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, whereby the coating film is cured to form a liquid crystal layer. From the standpoint of obtaining a good alignment, it is preferred to carry out these treatments in an overlapping manner. The heating temperature of the coating film is 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 preferred to carry out heating at a temperature ranging from 40 °C 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 to be irradiated is preferably set to 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably set to 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 manufacturing 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 if it is a quarter wave plate, the phase difference is selected. It has a thickness of 120 nm to 150 nm. The thickness of the liquid crystal layer in which the target phase difference can be obtained 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 as described above can be preferably used as a retardation film of a liquid crystal display element. The operation mode of the liquid crystal display element to which the retardation film produced by using the liquid crystal alignment agent of the present invention is applied is not limited, and can be applied to various well-known modes 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 to set the substrate of the retardation film to a TAC system or an acrylic substrate, and to use the substrate of the retardation film as a protective film for the polarizing film.

Here, a method of producing a retardation film on an industrial scale is a roll-to-roll method. The method is a method in which the following treatment is carried out in a continuous step, and the film after the steps is recovered as a wound body: the film is taken up from the wound body of the elongated substrate film, and the film is wound up A process of forming a liquid crystal alignment film on the film; a process of applying a polymerizable liquid crystal on the liquid crystal alignment film and performing hardening; and a process of laminating a protective film as needed. The phase difference film formed using the liquid crystal alignment agent of the present invention has good adhesion to the substrate, and even when it is stored as a wound body, the liquid crystal alignment film and the substrate are not easily peeled off. Therefore, it is possible to suppress a decrease in the yield of the product when the retardation film is produced by the roll-to-roll method, and it is also preferable from the viewpoint of productivity.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, for watches, portable game machines, word processors, notebook computers, car navigation systems, video cameras, personal digital assistants (PDAs), digital cameras, Various display devices such as mobile phones, smart phones, various monitors, LCD TVs, and information displays. [Examples]

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

In the following 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. Further, in the following, the compound represented by the formula X is simply referred to as "compound X". [Weight Average Molecular Weight Mw of Polymer] Mw is a polystyrene-converted value measured by GPC under the following conditions. Pipe column: TSKgelGRCXLII manufactured by Tosoh Co., Ltd. Solvent: Tetrahydrofuran Temperature: 40 ° C Pressure: 68 kgf/cm ² [Polyimide ratio of polymer] Put the solution containing polyimine into pure water The obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl hydrazine, and tetramethyl decane was used as a standard substance, and ¹ H-nuclear magnetic resonance (Nuclear Magnetic Resonance) was measured at room temperature. , NMR). The ¹ H-NMR spectrum obtained, the ratio (PEI) is obtained using the following Equation (EX-1). Ruthenium amination rate (%) = (1-A ¹ /A ² × α) × 100 (EX-1) (In the formula (EX-1), A ¹ is a source appearing near a chemical shift of 10 ppm The peak area of the proton in the NH group, A ² is the peak area derived from other protons, and α is the ratio of the number of other protons in the precursor of the polymer (polyproline) relative to one proton of the NH group) [Epoxy equivalent] The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105. [Solution 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 Compound> [Synthesis Example 1-1; Synthesis of Compound (X-1)] Compound (X-1) was synthesized according to the following Scheme 1. Further, "Boc" in the scheme means a third butoxycarbonyl group (the same applies hereinafter). [Chemistry 13]

[Synthesis Example 1-2; Synthesis of Compound (X-2)] Compound (X-2) was synthesized according to the following Scheme 2. [Chemistry 14]

[Synthesis Example 1-3; Synthesis of Compound (X-3)] Compound (X-3) was synthesized according to the following Scheme 3. [化15]

[Synthesis Example 1-4; Synthesis of Compound (X-4)] Compound (X-4) was synthesized according to the following Scheme 4. [Chemistry 16]

<Synthesis of Polymer> [Synthesis Example 2-1; Synthesis of Polymer (PA-1)] 10.68 g as a tetracarboxylic dianhydride (100 mols relative to the total amount of the diamine used for the synthesis) (91 moles) of pyromellitic dianhydride, and 1.15 g (same as 5 moles) of compound (X-4) as diamine, 16.55 g (same as 80 moles) of double [2- (4-Aminophenyl)ethyl]hexanedicarboxylic acid and 1.60 g (with 15 moles) of 4,4'-diaminodiphenylamine dissolved in 85 g of N-methyl-2- The reaction was carried out at 30 ° C for 6 hours in a mixed solvent of pyrrolidone (NMP) and 85 g of γ-butyrolactone (GBL). Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate thus collected was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 27.9 g of polylysine (hereinafter referred to as polymer (PA-1)). The obtained polymer (PA-1) was prepared in a solvent composition of NMP: GBL = 50:50 to be 15% by weight, and the viscosity of the solution was measured and found to be 461 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.

[Synthesis Example 2-2 to Synthesis Example 2-6] The same procedure as in Synthesis Example 2-1 was carried out except that the type and amount of the tetracarboxylic dianhydride and the diamine used in the reaction were changed as shown in Table 1 below. Polylysine (polymer (PA-2) to polymer (PA-6)). The polymer solutions obtained in Synthesis Example 2-2 to Synthesis Example 2-6 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.

[Table 1]

With respect to the numerical values in Table 1, tetracarboxylic dianhydride indicates the use ratio (mol%) relative to the total amount of the tetracarboxylic dianhydride used in the reaction, and the diamine indicates the total amount of the diamine used in the reaction. The proportion of use (% by mole). The abbreviations of the tetracarboxylic dianhydride and the diamine in Table 1 are as follows. (tetracarboxylic dianhydride) AN-1:1,2,3,4-cyclobutanetetracarboxylic dianhydride AN-2: pyromellitic dianhydride AN-3: 2,3,5-tricarboxyl ring Amyl acetal dianhydride AN-4: 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3 -Dione AN-5: 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan- 1,3-diketone AN-6: bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride (diamine) DA-1: Compound DA-2 represented by the formula (X-1): the compound DA-3 represented by the formula (X-2): the compound DA-4 represented by the formula (X-3): Compound DA-5 represented by X-4): bis[2-(4-aminophenyl)ethyl] adipate DA-6: 4,4'-diaminodiphenylamine DA-7: 3,5-diaminobenzoic acid DA-8: N-(2,4-diaminophenyl)-4-(4-heptylcyclohexyl)benzamide-3:4-(fourteen Alkoxy)benzene-1,3-diamine DA-10: cholesteryl 3,5-diaminobenzoate DA-11: 4,4'-diaminodiphenylmethane additionally, polymer (PA-4) is especially suitable for TN type liquid crystal display elements, and polymer (PA-5) is especially suitable for VA type liquid crystal display. (Including the PSA display).

[Synthesis Example 3-1; Synthesis of Polymer (PI-1)] 21.19 g as a tetracarboxylic dianhydride (98 mol parts relative to 100 mols of the total amount of the diamine used for the synthesis) Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, and 3.69 g (same as 10 moles) of compound as a diamine (X -4), 19.94 g (same as 60 moles) of bis[2-(4-aminophenyl)ethyl]adipic acid and 5.16 g (same as 30 moles) of 4,4'-diamine The diphenylamine was dissolved in 200 g of NMP and reacted at room temperature for 6 hours. Then, 250 g of NMP was added, 6.70 g of pyridine and 8.65 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 100 ° C for 5 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate thus collected was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain a polyimine (polymer (PI-1)) having a ruthenium iodide ratio of about 50%. The obtained polymer (PI-1) was prepared in an amount of 15% by weight in terms of NMP. The viscosity of the solution was measured and found to be 530 mPa·s. Further, the obtained 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.

[Synthesis Example 4-1; Synthesis of Polymer (p-1)] The polymer (p-1) was obtained by the same method as the method described in International Publication No. 2013/115228. First, 3.35 g (15.00 mmol) of a compound represented by the following formula (u-1) was weighed in a 50 ml four-necked flask equipped with a nitrogen gas introduction tube and a mechanical stirrer, and 34.8 g of NMP was added thereto to dissolve. Cool to about 10 ° C under a nitrogen atmosphere. Then, 2.85 g (14.60 mmol) of cyclobutanetetracarboxylic dianhydride was added in small portions, and the mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by weight polyisamic acid solution. The obtained polyaminic acid (polymer (p-1)) had a weight average molecular weight of 23,000. [化17]

[Synthesis Example 5-1; Synthesis of Polymer (PSi-1)] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl) was added. Ethyltrimethoxydecane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were mixed at room temperature. After 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, the mixture was refluxed and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and 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 in the form of a viscous transparent liquid. A polyorganosiloxane having an oxopropyl group is obtained. ¹ H-NMR analysis of the polyorganosiloxane having an oxiranyl group revealed that an oxopropyl group-like peak like a theoretical intensity was obtained in the vicinity of a chemical shift (δ) = 3.2 ppm. A side reaction of the oxyheteropropyl group did not occur in the reaction. 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 3 g of 4-phenoxycinnamic acid were added to a 100 mL three-necked flask. And 0.10 g of Eucalite (UCAT) 18X (trade name, manufactured by San-Apro Co., Ltd.), and reacted at 80 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into methanol, and the resulting precipitate was recovered, dissolved in ethyl acetate to prepare a solution, and the solution was washed with water three times, and then the solvent was distilled off, thereby whitening. In the form of a powder, 6.3 g of polyorganosiloxane (PSi-1) having an oxyheteropropyl group and a cinnamic acid structure was obtained. The polystyrene-equivalent weight average molecular weight Mw obtained by measuring the polyorganosiloxane (PSi-1) by GPC was 3,500.

<Preparation and evaluation of liquid crystal alignment agent> [Example 1: Friction-aligned FFS-type liquid crystal display element] (1) Preparation of liquid crystal alignment agent Polymer (PA-1) obtained in Synthesis Example 2-1 as a polymer Dissolved in a mixed solvent containing γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (GBL: NMP: BC = 40: 40: 20 (weight ratio)) Among them, a solution having a solid concentration of 4.5% by weight was prepared. This solution was filtered using a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent (R-1).

(2) Evaluation of coatability The prepared liquid crystal alignment agent (R-1) was applied onto a glass substrate using a spinner, prebaked for 1 minute using a hot plate at 80 ° C, and then replaced with nitrogen in the chamber. Heating was carried out for 1 hour in an oven at 200 ° C (post-baking), whereby a coating film having an average film thickness of 0.1 μm was formed. The coating film was observed with a microscope having a magnification of 100 times and 10 times, and the film thickness was uneven and the presence or absence of pinholes was examined. Regarding the evaluation, even when the film thickness was not observed, the film thickness unevenness and the pinholes were not observed as "good", and the film thickness unevenness and the needle were observed under a microscope of 100 times. In the case where at least one of the pores and 10 times of the microscope were not observed, the film thickness unevenness and the pinhole were regarded as "coatability", and the film thickness unevenness was clearly observed under a microscope of 10 times. In the case of at least one of the pinholes, evaluation was considered as "poor" in coating properties. In the present Example, even in the case of a microscope of 100 times, no film thickness unevenness and pinholes were observed, and the coatability was "good". (3) Evaluation of friction resistance The obtained coating film was carried out 7 times using a friction machine having a roller wound with a cotton at a roller rotation speed of 1000 rpm, a table moving speed of 20 cm/sec, and a hair pressing length of 0.4 mm. Friction treatment. The foreign matter (fragment of the coating film) by frictional scraping 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 measured. Regarding the evaluation, the case where the number of foreign matter is three or less is regarded as "good" in friction resistance, and that four or more and seven or less cases are regarded as "torque resistance", and eight or more cases are regarded as friction resistance. "Poor" to evaluate. As a result, the friction resistance of the coating film is "good"

(4) Fabrication of FFS type liquid crystal display element by rubbing treatment The FFS type liquid crystal display element 10 shown in Fig. 1 was produced. First, a bottom electrode 15 having no pattern, a tantalum nitride film as the insulating layer 14, and a glass substrate 11a having electrode pairs on one surface and having a comb-shaped patterned top electrode 13 are sequentially formed. The opposite glass substrate 11b to which no electrode is provided is used as a pair, and the liquid crystal alignment agent (R) prepared in the above (1) is coated on the surface of the glass substrate 11a having the transparent electrode and the surface of the opposite glass substrate 11b, respectively. -1) to form a coating film. Then, the coating film was prebaked for 1 minute using a hot plate at 80 ° C, and then heated in a nitrogen-substituted oven at 230 ° C for 15 minutes (post-baking) to form a coating film having an average film thickness of 0.1 μm. . A schematic plan view of the top electrode 13 used herein is shown in FIG. 2(a) is a plan view of the top electrode 13, and FIG. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2(a). In this embodiment, the line width d1 of the electrode is set to 4 μm, and the distance d2 between the electrodes is set to 6 μm. Further, the top electrode 13 is a four-system driving electrode using the electrode A, the electrode B, the electrode C, and the electrode D. The configuration of the driving electrodes used is shown in FIG. The bottom electrode 15 functions as a common electrode that acts on all of the four-system driving electrodes, and the regions of the four-system driving electrodes become pixel regions.

Then, each surface of the coating film formed on the glass substrate 11a and the glass substrate 11b is subjected to a rubbing treatment with cotton to obtain a liquid crystal alignment film 12. In Fig. 2(b), the rubbing direction of the coating film formed on the glass substrate 11a is indicated by an arrow. Then, after the brand name "XN-21-S" (manufactured by Mitsui Chemicals, Inc.) as a sealant is applied to the outer edge of the surface of the one of the substrates having the liquid crystal alignment film, the substrate is used as the substrate 11a. The rubbing directions of the substrates 11b are antiparallel to each other so as to be bonded to each other via a spacer having a diameter of 3.5 μm to cure the sealant. Then, liquid crystal MLC-6221 (manufactured by Merck) was injected between a pair of substrates from the liquid crystal injection port to form a liquid crystal layer 16. Further, on the outer surfaces of the substrate 11a and the substrate 11b, a polarizing plate (not shown) is bonded so that the polarization directions of the two polarizing plates are orthogonal to each other, whereby the liquid crystal display element 10 is produced.

(5) Evaluation of liquid crystal alignment property The presence or absence of an abnormal region of light and dark change when a voltage of 5 V was applied/released (ON/OFF) was observed by a microscope at a magnification of 50 times with respect to the manufactured FFS liquid crystal display device. . Regarding the evaluation, the case where the abnormal region was not observed was regarded as "good" in the liquid crystal alignment property, and the case where the abnormal region was observed was regarded as the liquid crystal alignment "defect" and evaluated. The liquid crystal alignment of the liquid crystal display element is "good". (6) Evaluation of voltage holding ratio With respect to the manufactured FFS type liquid crystal display device, a voltage of 5 V was applied at 23 ° C with an application time of 60 μsec and a span of 167 msec, and then measurement was performed for 1,000 msec from the application release. After the voltage holding ratio (VHR), the result was 95.4%. Further, the measuring device was VHR-1 manufactured by TOYO Technica.

(7) Evaluation of afterimage characteristics (DC afterimage evaluation) The produced liquid crystal display element was placed in an environment of 25 ° C and one atmosphere. The bottom electrode was used as the common electrode of all four system drive electrodes, and the potential of the bottom electrode was set to a potential of 0 V (ground potential). The electrode B and the electrode D were short-circuited to the common electrode and set to a 0 V application state, and a combined voltage including an AC voltage of 3.5 V and a DC voltage of 1 V was applied to the electrode A and the electrode C for 2 hours. Immediately after the lapse of 2 hours, a voltage of 1.5 V was applied to all of the electrodes A to D. Then, it is determined that the driving stress application region (the pixel region of the electrode A and the electrode C) and the driving stress non-applied region (the electrode B and the electrode D) are not visually recognized from the time when the voltage of 1.5 V of the alternating current is applied to all the driving electrodes. The time difference of the luminance of the pixel area is eliminated as the afterimage. In addition, the shorter the time, the less likely the residual image is to be generated. The case where the afterimage erasing time is less than 30 seconds is regarded as "good", and the case of 30 seconds or more and less than 120 seconds is regarded as "may", and the case of 120 seconds or more is regarded as "bad", and the evaluation is performed. The afterimage erasing time of the liquid crystal display element of the example was 2 seconds, and it was evaluated that the afterimage characteristics were "good". (8) Light resistance The voltage holding ratio was measured for the manufactured FFS liquid crystal display device in the same manner as in the above (6), and this value was defined as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an 80 ° C oven irradiated with a light-emitting diode (LED) lamp for 500 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. The voltage holding ratio was measured again for the liquid crystal cell after light irradiation in the same manner as described above. This value was taken as the voltage holding ratio (VHR _AFBL ) after light irradiation. The amount of decrease in voltage holding ratio ΔVHR _BL (%) was obtained from the following formula (EX-2), and evaluated as light resistance. ΔVHR _BL = ((VHR _{BF -} VHR _AFBL ) ÷ VHR _BF ) × 100 (EX-2) When ΔVHR is less than 3%, the light resistance is judged to be "good", and it is 3% or more and less than 5%. The case is judged as "OK", and the case of 5% or more is judged as "Poor". As a result, the liquid crystal display element of the present embodiment had a ΔVHR _BL of 1.2% and a light resistance of "good".

(9) Non-uniformity of the periphery of the sealant (frame unevenness tolerance) The FFS liquid crystal display element produced was stored under the conditions of 25 ° C and 50% RH for 30 days, and then driven with an AC voltage of 5 V. Observe the lighting status. Regarding the evaluation, if the difference in brightness (black fine lines or white fine lines) is not seen around the sealant, it is regarded as "good". If the difference in brightness is seen, the difference in brightness within 20 minutes after lighting is considered to be "OK". The case where the brightness difference is seen even after 20 minutes is regarded as "bad". As a result, the difference in luminance of the liquid crystal display element was not observed, and it was judged as "good".

[Example 2 to Example 7, Comparative Example 1, Comparative Example 2, and Reference Example] In the first embodiment, the solid content (polymer and additive) contained in the liquid crystal alignment agent was changed as shown in Table 2 below. A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the type and amount of the liquid crystal alignment agent were produced, and an FFS type liquid crystal display element was produced by a rubbing method and evaluated variously. The evaluation results are shown in Table 2 below. Further, in Examples 5 to 7 and Comparative Example 2, an additive was formulated in the liquid crystal alignment agent. In Table 2, the numerical value of the additive represents a compounding ratio (parts by weight) of the additive with respect to 100 parts by weight of the polymer component. Further, in the reference example, when 5 parts by weight of piperidine was added to 100 parts by weight of the polymer component, precipitation was carried out, and thus no subsequent study was conducted.

[Table 2]

In Table 2, the abbreviation of the additive is as follows. A-1: the compound represented by the formula (A-1): A-2: the compound represented by the formula (A-2): a-1: piperidine

As shown in Table 2, in the examples 1 to 7, the coating properties and the friction resistance of the liquid crystal alignment agent, and the liquid crystal alignment property, the voltage holding ratio (initial VHR), the afterimage characteristics, and the light resistance of the liquid crystal display device. And the uneven tolerance of the frame is the result of "good" or "can", and a balance of various characteristics is achieved. From these circumstances, it is known that a liquid crystal display element having high reliability and frame unevenness resistance can be obtained by a liquid crystal alignment agent containing a compound (A) having a specific heterocyclic structure. In addition, the evaluation of the DC afterimage characteristics of the obtained liquid crystal display element (the burn-in property called "DC afterimage" caused by the residual electric charge accumulated by application of a DC voltage) is also high. On the other hand, in Comparative Example 1 and Comparative Example 2, in the plurality of evaluation items among the liquid crystal alignment property, the voltage holding ratio, the afterimage characteristics, the light resistance, and the frame unevenness tolerance, the results were inferior to those of the examples.

[Example 8: Photo-aligned FFS-type liquid crystal display element] (1) Preparation of liquid crystal alignment agent The polymer (PA-2) obtained in Synthesis Example 2-2 as a polymer was dissolved in γ-butyrolactone ( a mixed solvent of GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (GBL: NMP: BC = 40:40:20 (weight ratio)), a solid concentration of 4.5 % by weight solution. This solution was filtered using a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent (R-8).

(2) Evaluation of coatability The prepared liquid crystal alignment agent (R-8) was applied onto a glass substrate using a spinner, and prebaked for 1 minute using a hot plate at 80 ° C, and then replaced with nitrogen in the chamber. Heating was carried out for 1 hour in an oven at 200 ° C (post-baking), whereby a coating film having an average film thickness of 0.1 μm was formed. When the applicability was evaluated in the same manner as in the above (2) of the first embodiment, the coating property of the coating film was "good". (3) Evaluation of the alignment property Using the Hg-Xe lamp and the glan-taylor prism for the obtained coating film, 300 J/m ² containing an open line of 313 nm was irradiated from the normal direction of the substrate. The alignment treatment is carried out by polarizing ultraviolet rays. The refractive index anisotropy α (nm) of the glass substrate with an alignment film was measured using a liquid crystal alignment film inspection apparatus (LayScan) manufactured by MORITEX. Regarding the evaluation, the case of 0.020 nm or more was regarded as "good", the case of less than 0.020 nm and 0.010 nm or more was regarded as "may", and the case of less than 0.010 nm was regarded as "poor". As a result, the substrate was α = 0.035 nm, and the alignment was "good".

(4) Production of FFS-type liquid crystal display device by photo-alignment method First, each surface of a pair of glass substrate 11a and glass substrate 11b similar to (4) of the first embodiment is coated with a rotator. The liquid crystal alignment agent (R-8) prepared in the above (1) was formed to form a coating film. Then, the coating film was prebaked in a hot plate at 80 ° C for 1 minute, and then heated in a nitrogen-substituted oven at 230 ° C for 15 minutes (post-baking) to form a coating film having an average film thickness of 0.1 μm. . A schematic plan view of the top electrode 13 used herein is shown in FIG. 4(a) is a plan view of the top electrode 13, and FIG. 4(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 4(a). In the present embodiment, a substrate having a top electrode having an electrode having a line width d1 of 4 μm and a distance d2 between electrodes of 6 μm was used. Further, the top electrode 13 is a four-system driving electrode (see FIG. 3) using the electrode A, the electrode B, the electrode C, and the electrode D in the same manner as in the first embodiment. Then, on each surface of the coating film, 300 J/m ² of polarized ultraviolet rays containing an open line of 313 nm was irradiated from the normal direction of the substrate using an Hg-Xe lamp and a Glan-Taylor prism to obtain a pair of liquid crystal alignment films. Substrate. In this case, the irradiation direction of the polarized ultraviolet light is set so as to be irradiated from the normal direction of the substrate, and the direction of the line segment on which the polarized surface of the polarized ultraviolet light is projected on the substrate is set to the direction of the two arrows in FIG. Light irradiation treatment is performed.

Then, on the outer periphery of the surface of the one of the substrates having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball of 5.5 μm in diameter is applied by screen printing to form a pair of substrates. The liquid crystal alignment film faces are opposed to each other, and the pressure is projected in parallel with the direction in which the polarized surface of the polarized ultraviolet light is projected on the substrate, and the adhesive is thermally cured at 150 ° C for 1 hour. Then, the liquid crystal "MLC-6221" manufactured by Merck was filled in the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Then, a polarizing plate was bonded to both outer surfaces of the substrate, thereby manufacturing an FFS type liquid crystal display element. At this time, one of the polarizing plates is attached in such a manner that the polarizing direction thereof is parallel to the direction in which the polarized ultraviolet light of the liquid crystal alignment film faces the projection direction of the substrate surface, and the other sheet is in the polarization direction thereof and the polarization direction of the previous polarizing plate. Attached in an orthogonal manner.

(5) Evaluation of liquid crystal alignment property The liquid alignment of the manufactured light distribution FFS liquid crystal display device was evaluated in the same manner as in (5) of the first embodiment. As a result, the liquid crystal alignment property of the liquid crystal display element is "good". (6) Evaluation of Voltage Retention Rate The voltage holding ratio (VHR) was measured for the produced photoalignment type FFS liquid crystal display device in the same manner as in (6) of the first embodiment, and the voltage holding ratio was evaluated. As a result, the VHR was 97.5%. (7) Evaluation of afterimage characteristics (DC afterimage evaluation) The afterimage characteristics of the produced photoalignment type FFS liquid crystal display device were evaluated in the same manner as in (7) of the first embodiment. As a result, the afterimage erasing time was 1 second, and it was evaluated that the afterimage characteristics were "good". (8) Light resistance The voltage holding ratios (VHR _BF and VHR _AFBL ) were measured in the same manner as in the above (8), and the light resistance of the liquid crystal display element was evaluated based on the change in the voltage holding ratio before and after the application of the optical stress. As a result, ΔVHR _BL was 0.6%, and it was judged that the light resistance was "good". (9) Unevenness tolerance around the sealant (frame unevenness tolerance) The frame unevenness resistance was evaluated in the same manner as in the above (9) of the first embodiment. As a result, the difference in luminance of the liquid crystal display element was not observed, and it was judged that the frame unevenness tolerance was "good".

[Example 9: retardation film] (1) Preparation of liquid crystal alignment agent 100 parts by weight of the polymer (PSi-1) obtained in Synthesis Example 5-1, and 10 parts by weight of the compound (A-1) were dissolved. In a mixed solvent containing propylene glycol monomethyl ether acetate (PGMEA), 2-butanone (MEK), and butyl acetate (BTLAC) (PGMEA: MEK: BTLAC = 30:30:40 (weight ratio)) A solution having a solid concentration of 4.5% by weight. This solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-9).

(2) Production of retardation film The prepared liquid crystal alignment agent (R-9) was applied on one surface of a TAC film as a substrate by a bar coater, and baked at 120 ° C for 2 minutes in an oven. A coating film having a film thickness of 100 nm was formed. Then, 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 a Hg-Xe lamp and a Glan-Taylor prism on the surface of the coating 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 coating film after light irradiation by a bar coater. A coating film of a polymerizable liquid crystal is formed. After baking for 1 minute in an oven adjusted to a temperature of 50 ° C, a non-polarized ultraviolet light of 1,000 mJ/cm ² containing a bright line of 365 nm was irradiated from the vertical direction on the surface of the coating film using an Hg-Xe lamp to polymerize. The liquid crystal is cured to form a liquid crystal layer, thereby producing a retardation film.

(3) Evaluation of liquid crystal alignment property The presence or absence of an abnormal region was observed by the phase difference film produced in the above (2) by a visual inspection under a crossed nicol and a polarizing microscope (magnification: 2.5 times). Evaluation of liquid crystal alignment. Regarding the evaluation, the case where the alignment was good at the time of visual observation and the abnormal region was not observed by the polarizing microscope was regarded as "good" in liquid crystal alignment, and the case where no abnormal region was observed by visual observation but the abnormal region was observed by a polarizing microscope was regarded as liquid crystal alignment. The "can" was evaluated by visual observation and observation of an abnormal region by a polarizing microscope as a "defect" in liquid crystal alignment. As a result, the retardation film was evaluated as "good" liquid crystal alignment.

(4) Adhesion The adhesion of the coating film formed of the liquid crystal alignment agent to the substrate was evaluated by using the retardation film produced in the above (2). First, an equally spaced spacer with a guide is used, and a slit is drawn from the surface of the liquid crystal layer side of the retardation film by a cutter knife to form 10 in a range of 1 cm × 1 cm. × 10 grid patterns. The depth of each slit is set to a middle portion from the surface of the liquid crystal layer to the thickness of the substrate. Then, after the cellophane tape is sealed so as to cover the entire surface of the lattice pattern, the transparent tape is peeled off. The notched portion of the peeled lattice pattern was observed by visual inspection under crossed Nicols and the adhesion was evaluated. Regarding the evaluation, the case where the peeling was not confirmed at the intersection of the portion along the slit line and the lattice pattern was regarded as "good", and the number of the lattices observed to be peeled off in the portion was relative to the overall lattice pattern. The case where the number is less than 15% is considered to be "adhesiveness", and the case where the number of the lattices which are observed to be peeled off is 15% or more with respect to the total number of the lattice patterns is regarded as the adhesion. "Poor" to evaluate. As a result, the retardation film was "good" in adhesion.

10‧‧‧Liquid display components
11a, 11b‧‧‧ glass substrate
12‧‧‧Liquid alignment film
13‧‧‧Top electrode
14‧‧‧Insulation
15‧‧‧ bottom electrode
16‧‧‧Liquid layer
A, B, C, D‧‧‧ electrodes
Section C1‧‧‧
D1‧‧‧ line width
D2‧‧‧ distance

Fig. 1 is a schematic configuration diagram of an FFS liquid crystal display device. 2 is a schematic plan view of a top electrode for fabricating a rubbed alignment type liquid crystal display element. 2(a) is a plan view of the top electrode, and FIG. 2(b) is a partial enlarged view of the top electrode. Fig. 3 is a view showing a four-system driving electrode. 4 is a schematic plan view of a top electrode for fabricating a photoalignment type liquid crystal display element. 4(a) is a plan view of the top electrode, and FIG. 4(b) is a partial enlarged view of the top electrode.

10‧‧‧Liquid display components

11a, 11b‧‧‧ glass substrate

12‧‧‧Liquid alignment film

13‧‧‧Top electrode

14‧‧‧Insulation

15‧‧‧ bottom electrode

16‧‧‧Liquid layer

Claims (14)

A liquid crystal alignment agent containing a compound (A) having a partial structure represented by the following formula (1), In the formula (1), R ¹ is a protecting group of an amine group; and two "*1" represent a bonding bond bonded to a hydrocarbon group. The liquid crystal alignment agent according to the above aspect of the invention, wherein the compound (A) is a compound having a nitrogen-containing heterocyclic structure containing a partial structure represented by the formula (1) in a ring skeleton. The liquid crystal alignment agent according to claim 1 or 2, wherein the compound (A) is selected from the group consisting of a polyimide precursor, a polyimine, a polyoxyalkylene, and a poly(methyl). At least one polymer of the group consisting of acrylates and polyesters. The liquid crystal alignment agent according to claim 1 or 2, which contains a specific polymer as the compound (A), wherein the specific polymer is selected from the group consisting of a polyimide precursor and a poly At least one of a group consisting of amines, and the specific polymer is obtained by using a diamine having a nitrogen-containing heterocyclic structure having a partial structure represented by the formula (1) in a ring skeleton for use in a reaction. Polymer. The liquid crystal alignment agent according to claim 1 or 2, which contains a specific polymer as the compound (A), wherein the specific polymer is selected from the group consisting of a polyimide precursor and a poly At least one of the groups consisting of amines, and the specific polymer is a polymer obtained by using at least one compound selected from the group consisting of the following compounds: bicyclo[2.2.1]heptane -2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentane Acetic acid dianhydride, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride. The liquid crystal alignment agent according to claim 1, wherein the compound (A) is an additive component having a molecular weight of 1,000 or less. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal alignment film which is formed by coating a liquid crystal alignment agent according to any one of claims 1 to 6 on a substrate, and irradiating the coating film with light And get. A liquid crystal alignment film obtained by applying a liquid crystal alignment agent according to any one of the first to sixth aspects of the invention to a substrate, followed by rubbing treatment. A liquid crystal display element comprising the liquid crystal alignment film according to any one of claims 7 to 9. A retardation film comprising the liquid crystal alignment film according to item 8 of the patent application. A method for producing a retardation film, comprising the steps of: coating a liquid crystal alignment agent according to any one of claims 1 to 6 on a substrate to form a coating film; Light irradiation is performed; and the polymerizable liquid crystal is coated on the coating film after the light irradiation and hardened. a polymer which is at least one polymer selected from the group consisting of a polyimide precursor and a polyimine, and which has a formula represented by the following formula (1) in the ring skeleton a partially-structured nitrogen-containing heterocyclic structure diamine is obtained by use in the reaction, In the formula (1), R ¹ is a protecting group of an amine group; and two "*1" represent a bonding bond bonded to a hydrocarbon group. A diamine having a nitrogen-containing heterocyclic ring structure having a partial structure represented by the following formula (1) in a ring skeleton, In the formula (1), R ¹ is a protecting group of an amine group; and two "*1" represent a bonding bond bonded to a hydrocarbon group.