TWI675067B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer, diamine, and tetracarboxylic dianhydride - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display film, a liquid crystal display element, a polymer, a diamine, and a tetracarboxylic acid. Dianhydride. The liquid crystal alignment agent contains a compound (P) having a partial structure represented by the following formula (1). (In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond)

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer, diamine and tetracarboxylic dianhydride

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a polymer and a compound.

Previously, as a liquid crystal display device, various driving methods, such as an electrode structure or physical properties of liquid crystal molecules used, and manufacturing steps, have been developed, such as a known twisted nematic (TN) type or a super twisted nematic ( Super Twisted Nematic (STN) type, Vertical Alignment (VA) type, In-Plane Switching (IPS) type, fringe field switching (FFS) type and other liquid crystal display elements. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As the material of the liquid crystal alignment film, polyamic acid or polyimide is generally used in terms of various characteristics such as heat resistance, mechanical strength, and affinity with liquid crystal.

In recent years, in order to further improve the display performance of liquid crystal display elements, various liquid crystal alignment agents have been proposed. For example, for the purpose of reducing afterimages, it has been proposed to form a liquid crystal alignment film using a liquid crystal alignment agent containing polyfluorene imine or a precursor thereof having a nitrogen atom in addition to the fluorenimine group (for example, refer to Patent Document 1).

Patent Document 1 proposes that a tetracarboxylic dianhydride including 1,2,3,4-cyclobutane tetracarboxylic dianhydride and a diamine including a diamine having a fluorene amine bond (-NH-CO-) The polyfluorinated acid obtained by the reaction and the fluorinated polymer of the polyfluorinated acid obtained by reacting a tetracarboxylic dianhydride with a diamine are contained in a liquid crystal alignment agent; and The ratio of the number of fluorene imine rings which the imidized polymer has is set to a specific range. In Patent Document 1, improvement in voltage holding performance and afterimage characteristics is achieved by using the liquid crystal alignment agent. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2009-294274

[Problems to be Solved by the Invention]

However, due to the high polarity of the amido bond and the poor solubility of the liquid crystal alignment agent to the solvent components, the storage stability of the liquid crystal alignment agent and the coatability (printability) to the substrate tend to be poor. Room for further improvement.

An object of the present invention is to provide a liquid crystal alignment agent for a liquid crystal alignment agent that has a good solubility of the components and can obtain a liquid crystal display element that exhibits good afterimage characteristics. [Technical means to solve the problem]

The inventors of the present invention have conducted active research in order to achieve the problems of the prior art as described above, and found that the problem can be solved by protecting the amido bond with a protecting group. Specifically, the following liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer, and compound are provided.

One aspect of the present invention is to provide a liquid crystal alignment agent containing a compound (P) having a partial structure represented by the following formula (1).

[Chemical 1] (In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond)

Another aspect is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent. In addition, a liquid crystal display element including the liquid crystal alignment film is provided. In addition, another aspect is to provide a polymer having polyamine, polyamidate, polyimide, or polyamine as a main skeleton and having a partial structure represented by the formula (1). In addition, a diamine having a partial structure represented by the formula (1) and a tetracarboxylic dianhydride having a partial structure represented by the formula (1) are provided. [Effect of the invention]

By protecting the amide bond in the compound having a amide bond (-NH-CO-) with a protective group and containing the amide bond in the liquid crystal alignment agent, the solubility in a solvent can be made good. This makes it possible to obtain a liquid crystal alignment agent excellent in storage stability or printability. In addition, the protective group introduced into the amido bond is removed by, for example, heating during film formation, acid or alkali conditions, or light irradiation, thereby regenerating a structure with high liquid crystal orientation after film formation, as a result, A liquid crystal display element having good afterimage characteristics was obtained.

Hereinafter, each component contained in the liquid crystal aligning agent of this invention, and the other component arbitrarily mix | blended as needed are demonstrated. <Compound (P)> The liquid crystal alignment agent of this invention contains the compound (P) which has a partial structure represented by following formula (1). [Chemical 2] (In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond)

Y ¹ in the formula (1) is not particularly limited as long as it is a protecting group protecting a fluorenyl group, a fluorenimine group, a urea group, or a urethane group, and examples thereof include heat and light. A monovalent organic group derived from at least one of acid, alkali and acid. Y ^{1 is} preferably a monovalent organic group that is removed by at least heat. As specific examples thereof, for example, a urethane-based protective group, a fluorenyl-based protective group, a fluorenimine-based protective group, and sulfonamide Department of protection and so on. Among these groups, a urethane-based protecting group is preferred, and specific examples thereof include a third butoxycarbonyl group, a benzyloxycarbonyl group, and 1,1-dimethyl-2-halide. Ethyloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl ) Ethoxycarbonyl and the like. Specific examples of Y ¹ include groups represented by the following formulae (7-1) to (7-5). [Chemical 3] (In the formulae (7-1) to (7-5), Ar ¹ is a monovalent aromatic ring group having 6 to 10 carbons, R ¹⁴ is an alkyl group having 1 to 12 carbons, and R ¹⁵ is a monovalent organic group ; "*" Represents a bonding bond to a nitrogen atom)

Ar ^{1 in} the formula (7-2) is a group obtained by removing one hydrogen atom from an aromatic ring having 6 to 10 carbon atoms. Specific examples include a phenyl group and a naphthyl group. Examples of the alkyl group having 1 to 12 carbon atoms of R ¹⁴ in formula (7-4) include methyl, ethyl, propyl, butyl, pentyl, and hexyl. These groups may be linear or May be branched. Examples of the monovalent organic group of R ¹⁵ 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 ^{15 is} preferably an aryl group having 6 to 10 carbon atoms, and more preferably an aromatic group such as a phenyl group or a naphthyl group. In addition, the groups represented by the formulae (7-1) to (7-4) can be deprotected by using not only heat but also light. In terms of a high release property by heat, or a point where a compound derived from Y ¹ detached by heating during film formation can be discharged to the outside of the film as a gas, Y ^{1 is} preferably aminomethyl. An acid ester-based protecting group is more preferably a third butoxycarbonyl group. The atom bonded by the bonding bond "*" in the formula (1) is preferably a carbon atom. The compound (P) may constitute at least a part of the polymer component of the liquid crystal alignment agent, or may be contained in the form of an additive different from the polymer component serving as the substrate.

[Polymer (P)] When the compound (P) is a polymer having a partial structure represented by the formula (1) (hereinafter also referred to as a "polymer (P)"), its main skeleton is not present. Specific limitations include, for example, polyamic acid, polyimide, polyamidate, polysiloxane, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, Poly (styrene-phenylcis-butenediamidoimine) derivatives, poly (meth) acrylates, polymers having azobenzene derivatives, etc. as the main skeleton, and the like. The polymer (P) is preferably a polymer having a partial structure represented by the formula (1) in the main chain in terms of the solubility of the polymer or the good afterimage characteristics of the obtained liquid crystal display element. Thing. Among these polymers, the polymer (P) is preferably selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyfluorene in terms of heat resistance, mechanical strength, and affinity with liquid crystal. At least one polymer (hereinafter also referred to as a "specific polymer") in the group consisting of amines, and the specific polymer is more preferably a polymer having a partial structure represented by the formula (1) in the main chain. . In addition, (meth) acrylate means including an acrylate and a methacrylate.

(Polyamic acid) When the polymer (P) is polyamino acid, the polyamino acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine. Specifically, [i] a method of synthesizing by polymerizing a tetracarboxylic dianhydride having a partial structure represented by the formula (1) in a monomer composition; [ii] a method of synthesizing A method for synthesis by polymerizing a diamine having a partial structure represented by the formula (1) in a bulk composition; [iii] a monomer composition containing a partial structure having the partial structure represented by the formula (1); A method for synthesizing a tetracarboxylic dianhydride and a diamine having a partial structure represented by the formula (1) by polymerization. In addition, a tetracarboxylic dianhydride having a partial structure represented by the formula (1) is hereinafter also referred to as a "specific tetracarboxylic dianhydride", and a dicarboxylic acid having a partial structure represented by the formula (1) Amines are also known as "specific diamines".

(Tetracarboxylic dianhydride) The specific tetracarboxylic dianhydride used in the synthesis of a polyamic acid is not particularly limited as long as it has a partial structure represented by the formula (1). In the case where the specific tetracarboxylic dianhydride has a structural portion connecting two acid anhydride groups as a main chain, it is preferable that the main chain includes a partial structure represented by the formula (1) in the main chain. Examples thereof include compounds represented by the following formula (2). [Chemical 4] (In formula (2), R ¹ , R ² and R ⁴ each independently represent a divalent organic group; R ³ is a single bond or a divalent organic group; Y ¹ is a protecting group; Z ¹ and Z ² are each independently expressed Trivalent organic group; m is an integer from 1 to 3, and k is 0 or 1)

Examples of the divalent organic group of R ¹ to R ⁴ in the formula (2) include a divalent hydrocarbon group having 1 to 20 carbon atoms; the methylene group of the hydrocarbon group is -O-, -S-, -CO-, -COO-, -COS-, -NR ^a- , -CO-NR ^a- , -NR ^a -CO-NR ^a- , -Si (R ^a ) _2- (where R ^a is a carbon number of 1 to 12 A monovalent hydrocarbon group or a protecting group), -N = N-, -SO ₂ -and the like; a divalent group substituted by at least one of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group with a halogen atom (fluorine atom, chlorine Atom, bromine atom, iodine atom, etc.), a divalent group substituted by a hydroxyl group, a cyano group, or the like; a divalent group having a heterocyclic ring, or the like.

Herein, the "hydrocarbon group" in the present specification means a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, the "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that are composed only of a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure, and not containing an aromatic ring structure. However, it does not necessarily need to consist only of the structure of an alicyclic hydrocarbon, and also includes the hydrocarbon group which has a chain structure in a part. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not necessarily need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in part.

As specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ , examples of the chain hydrocarbon group include a methylene group, an ethylidene group, a propanediyl group, a butadiyl group, a pentadiyl group, and an adipic group. Base, heptyl, octyl, nonadiyl, decanediyl, vinylidene, propylenediyl, butenediyl, etc .; alicyclic hydrocarbon groups include, for example, cyclohexyl; aromatic hydrocarbon groups, such as Examples: phenylene, phenylene, etc. The trivalent organic group of Z ¹ and Z ² is preferably a trivalent chain hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic ring group, and more preferably selected from the group consisting of a benzene ring, a naphthalene ring, a cyclopentane ring, and a cyclohexane ring. A ring group formed by removing three hydrogen atoms from one ring of the group. m is preferably 1.

Specific examples of the specific tetracarboxylic dianhydride include, for example, compounds represented by the following formulae (2-1) to (2-3). [Chemical 5] (In the formula, TMS represents a trimethylsilyl group.) In the synthesis of a polyamic acid, a specific tetracarboxylic dianhydride may be used alone or in combination of two or more.

Specific tetracarboxylic dianhydrides can be synthesized by appropriately combining general methods of organic chemistry. For example, Y ¹ can be synthesized by reacting a tetracarboxylic dianhydride having "-NH-CO-" with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine. Specific tetracarboxylic dianhydride of the third butoxycarbonyl group. However, the synthesis method of a specific tetracarboxylic dianhydride is not limited to the said method.

The tetracarboxylic dianhydride used in the methods [i] and [iii] may be only the specific tetracarboxylic dianhydride, but other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride may be used in combination. In the method of [ii], when synthesizing polyamic acid, another tetracarboxylic dianhydride is used as the tetracarboxylic dianhydride. Examples of other tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride;

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3 , 3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-c] furan-1, 3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2 , 5-Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl norbornyl Alkane-2: 3,5: 6-dianhydride, bicyclic [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclic [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 dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 1,3-propanediol bis (anhydromellitate), p-phenylene bis (Trimellitic acid monoester anhydride) and the like; examples of the aromatic tetracarboxylic dianhydride : In addition to pyromellitic dianhydride, the tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can be used. In addition, other tetracarboxylic dianhydrides may be used singly or in combination of two or more kinds.

From the viewpoint of liquid crystal alignment and the like, it is preferable that the other tetracarboxylic dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentylacetic acid. Dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-Dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, bicyclic [ 3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, p-phenylene bis (trimellitic acid mono Ester anhydride), and at least one compound in the group consisting of pyromellitic dianhydride. Relative to the total amount of tetracarboxylic dianhydride used in the synthesis of polyamic acid, the amount of these other preferred tetracarboxylic dianhydrides (the total amount when two or more are used) is preferably It is set to 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more.

(Diamine) As long as the specific diamine has a partial structure represented by the formula (1), the rest of the structure is not particularly limited, and it is preferable to use a structural portion connecting two primary amine groups as a main chain. It is a compound containing the partial structure represented by said Formula (1) in this main chain. Preferred specific examples include a compound represented by the following formula (3), a compound represented by the following formula (3A), and a compound represented by the following formula (3B). [Chemical 6] (In formula (3), R ⁵ , R ^6, and R ⁸ each independently represent a divalent organic group; R ⁷ is a single bond or a divalent organic group; Y ¹ is a protecting group; t is an integer from 1 to 3, and s 0 or 1)

[Chemical 7] (In formula (3A), Y ² and Y ³ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbons or a protecting group; wherein at least one of Y ² and Y ³ is a protecting group; R ¹¹ and R ¹² and R ¹⁴ each independently represent a divalent organic group, R ¹³ is a single bond or a divalent organic group; v is an integer of 1 to 3, and u is 0 or 1)

[Chemical 8] (In formula (3B), R ²¹ , R ²² and R ²⁴ each independently represent a divalent organic group; R ²³ is a single bond or a divalent organic group; Y ⁴ is a protecting group; x is an integer of 1 to 3)

Regarding the divalent organic group of R ⁵ to R ⁸ in the formula (3), the divalent organic group of R ¹¹ to R ¹⁴ in the formula (3A), and R ²¹ to R ²¹ in the formula (3B) As the divalent organic group of R ²⁴ , the description of the divalent organic group of R ¹ to R ⁴ in the formula (2) can be applied. Among them, R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ , R ²¹ and R ^{24 are} preferably phenylene or substituted phenylene. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, and the like. t, v, and x are each preferably 1. Specific examples of the specific diamine include compounds represented by the following formulae (3-1) to (3-20), and compounds (ADA1) to (ADA8), respectively. [Chemical 9] (Where TMS stands for trimethylsilyl)

[Chemical 10] [Chemical 11] (3-21) (wherein R ¹⁵ and R ¹⁶ each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 to 12, and a1 and a2 each independently represent 0 to 4 An integer, p is an integer from 1 to 12)

[Chemical 12] Moreover, when synthesizing a polyamidic acid, a specific diamine may be used individually by 1 type, and may use 2 or more types together.

When Y ¹ in the formula (1) is a group deprotected by light, for example, the reaction of the following scheme A can also be used as a light alignment by polarized or non-polarized ultraviolet radiation Used liquid crystal alignment agent. [Chemical 13] (In process A, "*" indicates a bonding key)

Specific diamines can be synthesized by appropriately combining general methods of organic chemistry. For example, Y ¹ can be synthesized by reacting a diamine having "-NH-CO-" with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine. Specific diamines for oxycarbonyl. However, the synthesis method of a specific diamine is not limited to the said method.

The diamine used in the methods [ii] and [iii] may be only a specific diamine, or a diamine other than the specific diamine may be used in combination. In the method of [i], when synthesizing polyamic acid, another diamine is used as the diamine.

Examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine-based organosiloxanes. As specific examples of these diamines, examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. , 1,3-bis (aminomethyl) cyclohexane, etc .; Examples of the alicyclic diamine include: 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) )Wait;

Examples of the aromatic diamine include dodecyloxydiamine benzene, tetradecyloxydiamine benzene, pentadecyloxydiamine benzene, cetyloxydiamine benzene, and octadecyl Alkoxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate, Lanosteryl diaminobenzoate, 3,6-bis (4-aminobenzyloxy) 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) ) Benzamidine by the following formula (E-1) [Chem. 14] (In the formula (E-1), X ^I and X ^II each independently represent a single bond, -O-, -COO-, or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single group. 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 do not become 0 at the same time. ) Compounds such as diamines containing an orientation group:

P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4 , 4'-diaminoazobenzene, 1,5-bis (4-aminophenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- ( 4-aminophenyl) ethyl] adipate, N, N-bis (4-aminophenyl) methylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diamine Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4 -(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylene diisopropyl) Diphenylamine, 4,4 '-(m-phenylene diisopropyl) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminobenzene (Oxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diamine Oxazole, N-methyl-3,6-diaminooxazole, N-ethyl-3,6-diaminooxazole, N-phenyl-3,6-diaminooxazole, N, N'-bis (4-aminophenyl) -biphenyl , N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -pyrazine, 3,5-di Other diamines such as aminobenzoic acid, etc. Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilazane; etc. The diamine described in Japanese Patent Laid-Open No. 2010-97188.

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). Examples of the group "-C _c H _{2c + 1} " include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, deca Trialkyl, tetradecyl, pentadecyl, hexadecyl, hexadecyl, octadecyl, nonadecanyl, eicosyl, and the like are preferably linear. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (E-1) include compounds represented by the following formulae (E-1-1) to (E-1-4). [Chemical 15] In addition, other diamines can be used alone or in combination of two or more of them.

When applied to a liquid crystal alignment agent for a TN, STN, or vertical alignment type liquid crystal display element, a group (alignment) capable of imparting liquid crystal alignment ability to a coating film may be introduced into a side chain of a polyamic acid. base). Examples of the alignment group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton with 17 to 51 carbon atoms, and Polycyclic structure groups and the like. The polyamidic acid having an alignment group can be obtained, for example, by polymerizing a diamine containing an alignment group in the monomer composition. When a diamine containing an alignment group is used, its blending amount is preferably 3 mol% or more, and more preferably 5 mol% to 70 mol, relative to the total diamine used in the synthesis. %.

When a liquid crystal alignment ability is imparted to a coating film formed of a liquid crystal alignment agent by a photo-alignment method, at least a part of the polyamic acid as the polymer (P) may be a polymer having a photo-alignment structure. . Specific examples of the photo-alignment structure include groups that exhibit photo-alignment by photoisomerization, photodimerization, photodecomposition, and the like. Specifically, for example, an azo-containing group containing an azo compound or a derivative thereof as a basic skeleton, a cinnamic acid-containing group containing cinnamic acid or a derivative thereof as a basic skeleton, or chalcone or Chalcone-containing groups whose derivatives are used as the basic skeleton, benzophenone-containing groups containing benzophenone or their derivatives as the basic skeleton, coumarin-containing groups containing coumarin or their derivatives as the basic skeleton Coumarin groups, cyclobutane-containing structures containing cyclobutane or its derivatives as the basic skeleton, bicyclic [2.2.2] octene or its derivatives containing the bicyclic [2.2.2] The structure and content of octene are given by the following formula (4): (In formula (4), X ³ represents a sulfur atom, an oxygen atom, or -NH-; "*" represents a bonding bond; wherein at least one of the two "*" s is bonded to an aromatic ring). Structure as a basic skeleton.

The polyamidic acid having a photo-alignment structure can be obtained, for example, by polymerizing at least one of a tetracarboxylic dianhydride having a photo-alignment structure and a diamine having a photo-alignment structure in a monomer composition. . In this case, from the viewpoint of photoreactivity, the use ratio of the monomer having a photo-alignment structure is preferably 20 mol% or more with respect to the total amount of the monomers used in the synthesis of the polymer. More preferably, it is set to 30 mol% to 80 mol%.

(Synthesis of Polyamic Acid) Polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine as described above together with a molecular weight modifier as necessary. The use ratio of the tetracarboxylic dianhydride and the diamine provided for the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 to 2 equivalents. It is more preferably a ratio of 0.8 to 1.2 equivalents. When synthesizing polyamidic acid as a polymer (P), the use of a specific tetracarboxylic dianhydride and a specific diamine is considered from the viewpoint of sufficiently improving the solubility improving effect of polyamic acid and the effect of reducing afterimages. The proportion is preferably 10 mol% or more, and more preferably 20 mol% to 80 mol, relative to the total amount of monomers used in the synthesis. Ear%, particularly preferably 25 to 70 mole%.

Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, phenyl isocyanate, and isocyanate. Monoisocyanate compounds such as acid naphthyl esters and the like. 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 tetracarboxylic dianhydride and diamine used.

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

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (organic solvent of the first group), or an organic solvent selected from the first group is preferably used. A mixture of one or more compounds selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvent of the second group). In the latter case, the ratio of the organic solvent in the second group to the total amount of the organic solvent in the first group and the second group is preferably 50% by weight or less, and more preferably 40% by weight. % Or less, particularly preferably 30% by weight or less.

Particularly preferred organic solvents are preferably those selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, and γ- One or more of the group consisting of butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol and halogenated phenol are used as a solvent, or these organics are used within the range of the ratio A mixture of one or more solvents with other organic solvents. The used amount of the organic solvent (a) is preferably an amount in which the total amount (b) of the tetracarboxylic dianhydride and diamine is 0.1% to 50% by weight relative to the total amount (a + b) of the reaction solution. .

In the manner as described above, a reaction solution obtained by dissolving polyamic acid was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamino acid contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamino acid can be purified and then Provided for preparation of liquid crystal alignment agent. Isolation and purification of a polyamic acid can be performed according to a well-known method.

(Polyamidate) The polyamidate as the polymer (P) can be obtained, for example, by a method in which a tetracarboxylic acid diester dihalide is reacted with a diamine. The "tetracarboxylic acid diester dihalide" in this specification refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified and the remaining two are halogenated. The "tetracarboxylic acid diester" refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified, and the remaining two are carboxyl groups.

The tetracarboxylic acid diester dihalide used can be obtained by reacting a tetracarboxylic acid diester with an appropriate chlorinating agent such as thionyl chloride. The tetracarboxylic diester can be reacted with, for example, tetracarboxylic dianhydride (specific tetracarboxylic dianhydride and other tetracarboxylic dianhydride) exemplified in the synthesis of polyamic acid with alcohols such as methanol or ethanol. obtain. Examples of the diamine that reacts with a tetracarboxylic acid diester dihalide include specific diamines and other diamines other than the specific diamines and other diamines exemplified in the description of the synthesis of polyamic acid. A compound in which the primary amine group is protected with a protecting group (hereinafter also referred to as "diamine compound CA1") and the like. Specific examples of the primary amine group-protected diamine compound (CA1) include a compound represented by the following formula (5). [Chemical 17] (In formula (5), R ⁹ is a divalent organic group, and Y ¹ is a protecting group; a plurality of Y ¹ may be the same or different)

The description of the divalent organic group of R ⁹ in the formula (5) can be applied to the description of the divalent organic group of R ¹ to R ⁴ in the formula (2). Specific examples of the compound represented by the formula (5) include compounds represented by the following formulae (5-1) to (5-16). [Chemical 18] [Chemical 19] [Chemical 20]

The use ratio of the tetracarboxylic diester dihalide and diamine provided to the polymer (P) synthesis reaction is preferably 1 equivalent to the amine group of the diamine, and the group of the tetracarboxylic diester dihalide " “-COX (X is a halogen atom)” is a ratio of 0.2 to 2 equivalents, and more preferably a ratio of 0.8 to 1.2 equivalents. From the viewpoint of sufficiently improving the improvement effect of the solubility of the polyamic acid and the effect of reducing the afterimage, the four having a partial structure represented by the above formula (1) with respect to the total amount of monomers used in the synthesis The use ratio of the carboxylic acid diester dihalide, the specific diamine, and the diamine compound (CA1) (the total amount in the case of using a plurality of types) is preferably 10 mol% or more, more preferably It is 20 mol% to 80 mol%, and more preferably 25 mol% to 70 mol%.

The reaction of the tetracarboxylic diester dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably -30 ° C to 150 ° C, and more preferably -10 ° C to 100 ° C. The reaction time is preferably from 0.1 to 48 hours, and more preferably from 0.5 to 36 hours. As the organic solvent used in the reaction, descriptions of organic solvents that can be used in the synthesis reaction of polyamic acid can be applied. The used amount of the organic solvent is preferably an amount in which the total amount of the tetracarboxylic diester dihalide and the diamine is 0.1 to 50% by weight based on the total amount of the reaction solution. The base used in the reaction can be preferably used, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine; sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, Alkali metals such as sodium and potassium. The amount of the alkali used is preferably 2 to 4 mol, and more preferably 2 to 3 mol relative to 1 mol of the diamine.

As described above, a reaction solution obtained by dissolving a polyamidate is obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamidate contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the isolated polyamidate can be purified. It is then provided to the preparation of the liquid crystal alignment agent. Isolation and purification of polyamidate can be performed according to a known method. The polyamidate may have only a pseudoamidate structure, or may be a partially esterified product in which a pseudoamidate structure and a pseudoamidate structure coexist. In addition, the polyamic acid ester as the polymer (P) is not limited to the synthesis method. For example, a method of reacting the polyamino acid as the polymer (P) with an alcohol may be used. It is obtained by a method of reacting a carboxylic acid diester with a diamine and the like.

(Polyimide) The polyimide as the polymer (P) can be obtained, for example, by dehydrating and ring-closing the polyamidate synthesized in the manner described above, and then imidating. In the case where the polyamidic acid is subjected to dehydration and ring closure to form a polyimide, the reaction solution of the polyamidic acid may be directly provided to the dehydration ring-closure reaction, or the polyamidic acid contained in the reaction solution may be separated It is then provided to the dehydration ring closure reaction, or the isolated polyamidic acid may be purified and then provided to the dehydration ring closure reaction.

The polyamidoimide may be a complete phosphonium imide obtained by dehydrating and ring-closing all the phosphonium structures of the polyphosphonium acid as a precursor thereof, or may be dehydrating and cyclizing only a part of the phosphonium structure. In addition, a part of the sulfonium imide compound in which the sulfonium acid structure and the sulfonium ring structure coexist. The polyimide used in the reaction has a hydrazone imidization rate of preferably 20% or more, more preferably 30% to 99%, even more preferably 40% to 99%. This fluorene imidization ratio is a total of the number of fluorene imine structures and the number of fluorene imine rings with respect to the total number of fluorene imine rings and the number of fluorene imine rings. Here, a part of the fluorene imine ring may be an isofluorene ring.

The dehydration ring closure of the polyamic acid is preferably performed by the following method: heating the polyamic acid; or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closing catalyst to the solution, Method of heating as needed. Among these methods, the latter method is preferred.

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

In this way, a reaction solution containing polyfluoreneimine was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the dehydrating agent and the dehydration ring-closing catalyst can be removed from the reaction solution and then provided to the preparation of the liquid crystal alignment agent, or the polyfluorene imide can be separated and then provided to the liquid crystal alignment agent. Preparation of the agent, or the isolated polyfluorene imide may be purified and then provided to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to a known method.

(Polyamine) The polyamine of the polymer (P) can be obtained, for example, by a method in which a dicarboxylic acid and a diamine are reacted. Here, it is preferred that the dicarboxylic acid is subjected to arsine chlorination using a suitable chlorinating agent such as thionyl chloride, and is then provided to the reaction with the diamine. The "dicarboxylic acid dihalide" as used herein refers to a compound in which two carboxyl groups of a dicarboxylic acid are halogenated.

The dicarboxylic acid used in the synthesis of polyamide is not particularly limited, and examples thereof include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, and 2-formaldehyde. Adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, Aliphatic dicarboxylic acids such as fumaric acid and muconic acid; cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, etc. have alicyclic Structure of dicarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2,5-dimethylterephthalic acid Dicarboxylic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4 ' -Diphenyl ether dicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3 '-[4,4'-(methylene di-p (Phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] dibutyric acid, 3,4-diphenyl-1,2-cyclobutane Dicarboxylic acids, azobenzene-4,4'-dicarboxylic acids, etc. are aromatic Dicyclic dicarboxylic acids and the like. The dicarboxylic acid dihalides may be used singly or in combination of two or more kinds. Examples of the diamine used in the synthesis of polyamine include a compound represented by the formula (5) and the like in addition to the specific diamine and other diamines exemplified in the description of the synthesis of polyamic acid. In this case, by using a specific diamine or a diamine compound (CA1) for at least a part of the monomer, polyamine as a polymer (P) can be obtained. The diamines may be used singly or in combination of two or more.

The use ratio of the dicarboxylic acid dihalide and the diamine provided to the polymer (P) synthesis reaction is preferably 1 equivalent to the amine group of the diamine, and the group of the dicarboxylic acid dihalide "-COX (X (Halogen atom) "is a ratio of 0.2 to 2 equivalents, and more preferably a ratio of 0.8 to 1.2 equivalents.

The reaction of a dicarboxylic acid dihalide and a diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably 0 ° C to 200 ° C, and more preferably 10 ° C to 100 ° C. The reaction time is preferably 0.5 to 48 hours, and more preferably 1 to 36 hours. The organic solvent used in the reaction is preferably an organic solvent. For example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylmethane, N- Methyl-2-pyrrolidone and the like. The used amount of the organic solvent is preferably 400 to 900 parts by weight, and more preferably 500 to 700 parts by weight based on 100 parts by weight of the total amount of the dicarboxylic acid dihalide and diamine. The base used in the reaction can be preferably used, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine; lithium hydride, sodium hydride, potassium hydride, bis (trimethyl Silyl) lithium ammonium, sodium bis (trimethylsilyl) ammonium, potassium bis (trimethylsilyl) ammonium, lithium diisopropylammonium, sodium diisopropylammonium, diisopropyl Alkali metals such as potassium sulfonamide and third butyl lithium. The amount of the alkali used is preferably 2 to 4 mol, and more preferably 2 to 3 mol relative to 1 mol of the diamine.

In this manner, a reaction solution obtained by dissolving polyfluorene is obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamide contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamine can be purified and then provided to the liquid crystal alignment agent. Preparation of liquid crystal alignment agent. Isolation and purification of polyamine can be performed by a known method.

The solution viscosity and weight average molecular weight (Mw) of the polymer (P) can be appropriately selected according to the main skeleton. For example, in the case of polyamidic acid, polyamidate, polyimide, and polyamidamine, the solution viscosity of the polymer is preferably such that when it is made into a solution having a concentration of 10% by weight, it has Those having a solution viscosity of 10 mPa · s to 800 mPa · s are more preferably those having a solution viscosity of 15 mPa · s to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the polymer (P) is a concentration of 10 prepared by using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer (P). A weight% polymer solution was measured at 25 ° C using an E-type viscometer. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, and more preferably 10 or less.

[Compound (P) as an Additive] When the compound (P) is used as an additive, a compound having a partial structure represented by the formula (1) may preferably be a compound having a plurality of photopolymerizable groups ( Hereinafter, it is also called "photopolymerizable compound (P)"). As a preferable specific example, the compound etc. which are represented by following formula (6) are mentioned, for example. [Chemical 21] (In formula (6), X ⁴ and X ⁵ are photopolymerizable groups; R ¹⁰ , R ¹¹ and R ¹³ each independently represent a divalent organic group, R ¹² is a single bond or a divalent organic group; Y ¹ is a protection Base; f is an integer from 1 to 3, and g is 0 or 1)

Examples of the photopolymerizable group of X ⁴ and X ⁵ in the formula (6) include a group having a polymerizable unsaturated bond, and the like. Specific examples include (meth) acrylfluorenyloxy, styryl, (meth) acrylfluorenylamino, vinyl, CH ₂ = C (CH ₃ )-, and vinyloxy (CH ₂ = CH-O-), a group represented by the following formula (x-1) or formula (x-2), and the like. [Chemical 22] (In formula (x-1), X ⁶ is an oxygen atom or -NH-; "*" represents a bonding bond)

In terms of high photoreactivity, the photopolymerizable group is preferably a (meth) acrylfluorenyloxy group. The (meth) acrylfluorenyloxy group includes a meaning of "acrylfluorenyloxy" and "methacrylfluorenyloxy". The (meth) acrylamido group has a meaning including "acrylamido" and "methacrylamido".

The description of the divalent organic group of R ¹⁰ to R ¹³ can be applied to the description of the divalent organic group of R ¹ to R ⁴ in the formula (2). As R ¹⁰ to R ¹³ , from the viewpoint of affinity with liquid crystals, it is preferable that at least any one of these R ¹⁰ to R ¹³ is a phenylene group, a cyclohexyl group, or a phenylene group, and more preferably Two or more of R ¹⁰ to R ^{13 are} a phenylene group, a cyclohexyl group, or a phenylene group. From the viewpoint of the solubility of the compound (P), it is preferred that at least any one of R ¹⁰ to R ¹³ is a cyclohexyl group. f is preferably 1. Specific examples of the photopolymerizable compound (P) include compounds represented by the following formulae (6-1) to (6-30). [Chemical 23] [Chemical 24] (In formulas (6-1) to (6-20), R is a hydrogen atom or a methyl group, and n is an integer of 1 to 20; Boc represents a third butoxycarbonyl group) [Chem. 25] (In formulae (6-21) to (6-24), n is an integer of 1 to 20; Boc represents a third butoxycarbonyl group) [Chem. 26] (In formulas (6-25) to (6-30), R is a hydrogen atom or a methyl group, and m and n each independently represent an integer of 1 to 20; Boc represents a third butoxycarbonyl group)

In the liquid crystal alignment agent, the compounding ratio of the compound (P) as an additive is preferably 1 to 100 parts by weight, and more preferably 5 to 50 parts by weight based on 100 parts by weight of the total weight of the polymer component. Parts by weight. In addition, the compound (P) may be used singly or in combination of two or more kinds. The molecular weight of the compound (P) is preferably 1,500 or less, more preferably 1,200 or less, and even more preferably 1,000 or less.

<Other components> The liquid crystal aligning agent of this invention may contain other components other than a compound (P) as needed. Examples of the other components include polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy-containing compounds"), functional silane compounds, and the like.

[Other polymers] The other polymers may be used for the purpose of improving various characteristics such as solution characteristics, electrical characteristics, heat resistance, and mechanical strength, or for the purpose of cost reduction and the like. The other polymer is a polymer which does not have a partial structure represented by the formula (1), and examples thereof include polyamic acid, polyimide, polyamidate, polyorganosiloxane, polysiloxane Esters, polyamidoamines, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide diimines) derivatives, or poly (meth) acrylates A polymer having a skeleton and not having the specific structure. Among these polymers, at least one polymer selected from the group consisting of polyamidic acid, polyamidoimide, polyamidate, and polyamidoamine can be preferably used for other polymers.

When other polymers are blended in the liquid crystal alignment agent, the blending ratio is preferably appropriately selected according to the type of the compound (P). For example, when the compound (P) is a polymer, the blending ratio of other polymers is 100 parts by weight with respect to the total of the polymers contained in the liquid crystal alignment agent (the total of the polymer (P) and other polymers). It is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and even more preferably 0.1 to 30 parts by weight. When the liquid crystal alignment agent of the present invention contains the compound (P) as an additive, the liquid crystal alignment agent contains at least one polymer selected from the group consisting of a polymer (P) and other polymers as a polymer. ingredient. The blending ratio of other polymers in this case can be arbitrarily set within a range of 100% by weight or less with respect to the total amount of the polymers contained in the liquid crystal alignment agent. It is preferably 10% by weight to 100% by weight, and more preferably 30% by weight to 90% by weight.

[Epoxy Group-Containing Compound] The epoxy group-containing compound can be used in order to improve the adhesiveness or electrical characteristics of the liquid crystal alignment film to the substrate surface. Examples of such epoxy-containing compounds include the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopenta Glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl -Aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine and the like. Other examples of the epoxy group-containing compound include an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598. When an epoxy group-containing compound is blended in a liquid crystal alignment agent, the blending ratio is preferably 40 parts by weight or less with respect to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent, and more preferably It is set to 0.1 to 30 parts by weight.

[Functional Silane Compound] The functional silane compound can be used for the purpose of improving the printability of a liquid crystal alignment agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyl Triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxy Silylpropyltriethylene triamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetic acid Ester, 9-trimethoxysilyl-3,6-diazanonanoic acid methyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethyl Oxysilane, glycidyloxymethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like. When other functional silane compounds are blended in the liquid crystal alignment agent, the blending ratio is preferably 2 parts by weight or less with respect to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent, and more preferably It is set to 0.02 parts by weight to 0.2 parts by weight.

In addition, as other components, in addition to the above, a compound or an antioxidant having at least one oxetanyl group in the molecule, a metal chelate compound, a hardening accelerator, a surfactant, a filler, a dispersant, Light sensitizers, etc.

The liquid crystal alignment agent of the present invention may contain only one polymer as a polymer component, or may contain two or more polymers. The preferable aspect in the case of containing two or more types of polymers includes the following [1] to [3] and the like. [1] Containing a polymer (P) and other polymers, and the polymer (P) and other polymers are at least one selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamido Appearance. [2] It contains a plurality of polymers (P), and the plurality of polymers (P) are in a form of at least one selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamidine. [3] A state in which a plurality of other polymers are contained, and the other polymers are at least one selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamidine (including the compound (P) As an additive). Among these aspects, in the aspect of [1], it is presumed that: in the polymer (P), the amine group in the amidine bond is protected by Y ¹ , then the polymer (P) and other polymers are The difference in polarity between them becomes large, and the dispersion of the polymer distribution can be sufficiently generated in the liquid crystal alignment film.

The compounding ratio of the compound (P) is preferably appropriately selected depending on the type of the compound (P) with respect to the solid components (components other than the solvent of the liquid crystal alignment agent) in the liquid crystal alignment agent. For example, when the compound (P) is a polymer, it is preferable to set the blending ratio of the polymer (P) to 40 parts by weight or more with respect to the total weight of solid components in the liquid crystal alignment agent. It is preferably 50 parts by weight or more, and more preferably 60 parts by weight or more. In addition, from the viewpoint of sufficiently obtaining the effects of the present invention and achieving cost reduction, the polymer (P1) and the other polymers in the aspect [1] in the aspect [1] are 100 parts by weight in total. P) The blending ratio is preferably 1 to 99 parts by weight, more preferably 10 to 90 parts by weight, and even more preferably 20 to 80 parts by weight. When the compound (P) is an additive, it is more preferable to set the compounding ratio of the compound (P) to 0.5 to 50 parts by weight based on 100 parts by weight of the total weight of the solid content in the liquid crystal alignment agent. It is preferably 2 to 30 parts by weight, and more preferably 5 to 25 parts by weight.

<Solvent> The liquid crystal alignment agent of the present invention is prepared as a liquid composition in which the compound (P) and other components used as necessary are dispersed or dissolved in a suitable solvent.

Examples of the organic solvent used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, and N, N-dimethylethyl Amine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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 Diethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These organic solvents may be used 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 components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably 1 The range is from 10% by weight to 10% by weight. That is, the liquid crystal alignment agent is applied to the surface of the substrate by a method described later, and preferably is heated to form a coating film as a liquid crystal alignment film or a coating film as 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 becomes too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, there are cases where the viscosity of the liquid crystal alignment agent increases and the coating property decreases. tendency.

A particularly preferable range of the solid content concentration varies depending on the method used when the substrate is coated with a liquid crystal alignment agent. For example, when the substrate is applied by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is particularly preferably 1.5 weight. % To 4.5% by weight. When using the printing method, it is particularly preferable that the solid content concentration is set to a range of 3% to 9% by weight, and thus the solution viscosity is set 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% to 5% by weight, thereby setting the solution viscosity to a range of 3 mPa · s to 15 mPa · s. The temperature when preparing the liquid crystal alignment agent is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C.

<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 described above. The operation mode of the liquid crystal display element is not particularly limited. For example, it can be applied to TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, and Optically Compensated Bend. , OCB) type and other operating modes.

The liquid crystal display element can be manufactured, for example, by the following steps (1) to (3). Step (1) uses different substrates according to the required operation mode. Step (2) and step (3) are common in each operation mode.

[Step (1): Formation of Coating Film] First, a liquid crystal alignment agent is coated on a substrate, and then the coating surface is heated to form a coating film on the substrate. (1-A) When manufacturing, for example, a TN-type, STN-type, or VA-type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are used as a pair, and the transparent conductive films are provided on each The forming surface is preferably coated with a liquid crystal alignment agent by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. For the substrate, for example, glass such as float glass and soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, and poly (alicyclic olefin) can be used. Transparent substrate. The transparent conductive film provided on one side of the substrate may be a NESA film (registered trademark of the American PPG Corporation) containing tin oxide (SnO ₂ ), or an indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium tin oxide (ITO) film, etc. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern by photoetching after forming a patternless transparent conductive film; a method of using a mask having a desired pattern when forming a transparent conductive film Wait. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface on which the coating film is formed may be coated with a functional silane compound, a functional titanium compound, or the like in advance. Pre-processing.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing the applied liquid crystal alignment agent from sagging or the like. The pre-baking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, in order to completely remove the solvent, and if necessary, perform a thermal sulfidation of the fluorinated acid structure present in the polymer, a sintering (post-baking) step is performed. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-B) When manufacturing an IPS-type or FFS-type liquid crystal display element, a liquid crystal alignment agent is applied to an electrode formation surface of a substrate provided with an electrode and a surface of a counter substrate not provided with an electrode, and then to each The coated surface is heated to form a coating film, wherein the electrode includes a transparent conductive film or a metal film patterned into a comb-tooth shape. Material of substrate and transparent conductive film used at this time, coating method, heating conditions after coating, patterning method of transparent conductive film or metal film, pretreatment of substrate, and preferred film of formed coating film The thickness is the same as described (1-A). As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the cases (1-A) and (1-B), after the liquid crystal alignment agent is coated on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. . In this case, when the polymer contained in the liquid crystal alignment agent is a polyamidic acid, a polyamidate, or a fluorinated polymer containing a fluorinated imine ring structure and a fluorinated acid structure Next, a further dehydration ring-closing reaction is performed by further heating after the coating film is formed, thereby forming a coating film that is further imidized.

[Step (2): Alignment Process] In the case of manufacturing a TN, STN, IPS, or FFS liquid crystal display element, a process (alignment) for imparting liquid crystal alignment ability to the coating film formed in the step (1) is performed. deal with). As a result, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. Examples of the alignment treatment include a rubbing treatment and a photo-alignment treatment. The rubbing treatment is performed by rubbing a coating film in a certain direction with a roller wound with a cloth containing fibers such as nylon, rayon, and cotton, thereby imparting a coating film. Liquid crystal alignment capability; The photo-alignment treatment irradiates a coating film formed on a substrate with light and imparts liquid crystal alignment energy to the coating film. On the other hand, in the case of manufacturing a vertical alignment type liquid crystal display element, the coating film formed in the step (1) may be directly used as a liquid crystal alignment film, or an alignment treatment may be performed on the coating film.

The light irradiation in the photo-alignment treatment can be performed by the following methods: (1a) a method of irradiating a coating film after post-baking; (2a) a method of irradiating a coating film after pre-baking and before post-baking (3a) A method of irradiating a coating film while heating the coating film in at least one of pre-baking and post-baking, and the like.

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

In addition, the liquid crystal alignment film after the rubbing treatment may be further processed to make the liquid crystal alignment film have a different liquid crystal alignment energy in each region: by irradiating a part of the liquid crystal alignment film with radiation, the A process of changing the pretilt angle of a part of the area; or a process of removing the resist film after forming a resist film on a part of the surface of the liquid crystal alignment film, and then performing a rubbing treatment in a direction different from the previous rubbing treatment. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved.

When manufacturing a polymer sustained alignment (PSA) type liquid crystal display device, or when using a liquid crystal alignment agent containing a polymerizable group-containing component to form a coating film, the step (1) can be used directly. The following step (3) is performed on the coating film formed in the method, but for the purpose of controlling the collapse of the liquid crystal molecules and performing the alignment division by a simple method, alignment processing such as weak rubbing treatment may be performed. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitable for a PSA type liquid crystal display element.

[Step (3): Construction of liquid crystal cell] (3-A) Two substrates having the liquid crystal alignment film formed in the manner described above are prepared, and liquid crystal is arranged between the two substrates disposed opposite to each other, thereby manufacturing a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, the two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded with a sealant, and the cells divided by the substrate surface and the sealant After the liquid crystal is injected into the gap, the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. A predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, a UV-curable sealant, and the liquid crystal is added dropwise to a predetermined number of locations on the liquid crystal alignment film. The liquid crystal alignment film is bonded to another substrate in a facing manner, and the liquid crystal is spread on the entire surface of the substrate, and 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 method, it is desirable that the liquid crystal cell manufactured as described above is further heated to a temperature at which the used liquid crystal obtains an isotropic phase, and then slowly cooled to room temperature, thereby eliminating the liquid crystal. Flow alignment during filling.

As the sealant, for example, an epoxy resin containing a hardener and alumina balls as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and dish liquid crystals. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, and biphenyl liquid crystals can be used. , Phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, and cubane-based liquid crystal Wait. In addition, these liquid crystals may be used by adding the following substances: cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate ); Chiral agents sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxymethylene-p-amino-2-methylbutane Ferroelectric liquid crystals such as cinnamate.

(3-B) When manufacturing a PSA-type liquid crystal display element, a liquid crystal cell is constructed in the same manner as described in (3-A) except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Then, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films included in the pair of substrates. The voltage applied here may be, for example, 5 V to 50 V DC or AC. In addition, as the light to be irradiated, ultraviolet rays including visible light with a wavelength of 150 nm to 800 nm and visible rays may be used, and ultraviolet rays including light with a wavelength of 300 nm to 400 nm are preferably used. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the preferable wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, and the like. The light irradiation amount is preferably 1,000 J / m ² to 200,000 J / m ² , and more preferably 1,000 J / m ² to 100,000 J / m ² .

(3-C) When a liquid crystal alignment agent containing a polymer component or a compound having a photopolymerizable group as an additive is used to form a coating film on a substrate, the following method may be adopted: 3-A) A liquid crystal cell is constructed in the same manner, and a liquid crystal display element is manufactured by applying light to the liquid crystal cell in a state where a voltage is applied between the conductive films of a pair of substrates. According to this method, the advantages of the PSA mode can be realized with a small amount of light irradiation. The description of (3-B) can be applied to the applied voltage or the conditions of the light to be irradiated.

Next, a polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain a liquid crystal display element. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called an “H film” with a protective cellulose acetate film or a polarizing plate including the H film itself. "H film" is a film formed by absorbing iodine while extending the orientation of polyvinyl alcohol.

The liquid crystal display element of the present invention can be effectively applied to a variety of devices, such as: clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants (Personal Digital Assistant, PDA), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices. [Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

In the following examples, the following methods were used to measure the weight average molecular weight Mw of the polymer, the amidation ratio, and the solution viscosity of the polymer solution. In addition, the compound represented by Formula X may be abbreviated as "compound X" below. [Weight average molecular weight of polymer Mw] Mw is a polystyrene conversion value measured by GPC under the following conditions. Column: manufactured by Tosoh Corporation, TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40 ° C Pressure: 68 kgf / cm ² [Polyimide ratio of polymer] A solution containing polyimide is charged into pure water, and the obtained After the precipitate was sufficiently dried under reduced pressure at room temperature, the precipitate was dissolved in deuterated dimethylsulfine, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. Based on the obtained ¹ H-NMR spectrum, the fluorene imidization ratio was determined using the following formula (1).醯 Imination ratio (%) = (1-A ¹ / A ² × α) × 100 ... (1) (In the formula (1), A ¹ is a NH-group-derived compound that appears near a chemical shift of 10 ppm. Proton peak area, A ² is the peak area derived from other protons, α is the ratio of other protons to the number of one proton of the NH group in the polymer precursor (polyamic acid)) [Polymer solution Solution viscosity] Using an E-type rotational viscometer, the solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. [Surface contact angle of film] Using a contact angle meter DM-700 manufactured by Kyowa Interface Chemical Co., Ltd., a droplet of ultra-pure water of about 2.0 μL was hung on a mold (ASL-400). The state of the droplets after the second was subjected to image processing to thereby measure the surface contact angle of the film.

<Synthesis of Compound> [Synthesis Example 1-1: Synthesis of Compound (I)] Compound (I) was synthesized according to the following scheme 1. [Chemical 27]

2.5 g of 4-nitro-N- (4-nitrophenyl) benzamidine was suspended in 30 mL of THF, and 1.5 g of N, N-dimethylaminopyridine was added thereto. To this solution was added 3.95 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring at room temperature for 3 hours, the suspended solid was filtered, and the solid was washed with ethanol. This solid was dried to obtain 2.2 g of a compound (i-1) with a purity of 99%. A three-necked flask containing 0.3 g of Pd / C was purged with nitrogen, and 40 ml of THF deaerated with oxygen was added thereto, followed by stirring. 2.2 g of compound (i-1) was added to the container, cooled to 0 ° C and stirred for 5 minutes. Hydrogen was introduced thereinto to reduce the nitro group. After stirring under a hydrogen atmosphere for 3 hours, 50 mL of THF was added, the reaction solution was filtered, and then the reaction solution was concentrated. The precipitated solid was recovered and dried to obtain 1.7 g of the target compound (I) with a purity of 99%.

[Synthesis Example 1-2: Synthesis of Compound (II)] Compound (II) was synthesized according to the following scheme 2. [Chemical 28]

2.8 g of N ¹ , N ⁶ -bis (4-nitrophenethyl) hexanediamine were suspended in 40 mL of THF, and 2.5 g of N, N-dimethylaminopyridine was added thereto. To this solution was added 16 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring at room temperature for 3 hours, the suspended solid was filtered, and the solid was washed with ethanol. This solid was dried to obtain 3.5 g of compound (ii-1) with a purity of 98%. A three-necked flask containing 0.5 g of Pd / C was purged with nitrogen, and 100 ml of THF deaerated with oxygen was added thereto, followed by stirring. 3.5 g of compound (ii-1) was added to the container, cooled to 0 ° C and stirred for 5 minutes. Hydrogen was introduced thereinto to reduce the nitro group. After stirring under a hydrogen atmosphere for 6 hours, 50 mL of THF was added, the reaction solution was filtered, and the reaction solution was concentrated. The precipitated solid was recovered and dried to obtain 2.8 g of the target compound (II) with a purity of 99%.

[Synthesis Example 1-3: Synthesis of Compound (III)] Compound (III) was synthesized according to the following scheme 3. [Chemical 29]

2.5 g of 4-nitro-N- (4-nitrophenyl) benzamide was suspended in 30 mL of THF, and 1.5 g of N, N-dimethylaminopyridine was added thereto. To this solution was added 10.4 g of N- [2- (trimethylsilyl) ethoxycarbonyloxy] butanediimide. After stirring at room temperature for 3 hours, the suspended solid was filtered, and the solid was washed with ethanol. This solid was dried to obtain 1.8 g of compound (iii-1) with a purity of 98%. A three-necked flask containing 0.3 g of Pd / C was purged with nitrogen, and 40 ml of THF deaerated with oxygen was added thereto, followed by stirring. 1.8 g of compound (iii-1) was added to the container, cooled to 0 ° C and stirred for 5 minutes. Hydrogen was introduced thereinto to reduce the nitro group. After stirring under a hydrogen atmosphere for 3 hours, 50 mL of THF was added, the reaction solution was filtered, and the reaction solution was concentrated. The precipitated solid was recovered and dried to obtain 1.5 g of the target compound (III) with a purity of 99%.

[Synthesis Example 1-4: Synthesis of compound (IV)] Compound (IV) was synthesized according to the following scheme 4. [Chemical 30]

5.0 g of bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) = 1,1'-biphenyl-4,4'-diyl ester was suspended in In 60 mL of THF, 0.5 g of N, N-dimethylaminopyridine was added thereto. To this solution was added 40 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring at room temperature for 7 hours, 10 mL of acetic anhydride was added and reacted for 5 hours. The suspended solid produced in the reaction was filtered, and the solid was washed with ethyl acetate. This solid was dried to obtain 4.5 g of compound (IV) with a purity of 97%.

[Synthesis Example 1-5: Synthesis of compound (V)] The compound (V) was synthesized according to the following scheme 5. [Chemical 31]

3.7 g of 4,4 '-(pentane-1,5-diylbis (oxy) bis (N- (4-nitrophenyl) benzidine) was suspended in 60 mL of THF, and To this was added 2.7 g of N, N-dimethylaminopyridine. To this solution was added 20 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring at room temperature for 5 hours, the suspended solid was filtered The solid was washed with ethanol. The solid was dried to obtain 3.7 g of compound (v-1) with a purity of 98%. A three-necked flask containing 0.3 g of Pd / C was replaced with nitrogen, and oxygen degassing was added thereto. 100 mL of THF was stirred. 3.7 g of compound (v-1) was added to the container, cooled to 0 ° C and stirred for 5 minutes. Hydrogen was introduced thereinto to reduce the nitro group. Under a hydrogen environment After stirring for 6 hours, 80 mL of THF was added, the reaction solution was filtered, and then the reaction solution was concentrated. The precipitated solid was recovered and dried to obtain 3.0 g of the target compound (V) with a purity of 99%.

[Synthesis Example 1-6: Synthesis of Compound (VI)] Compound (VI) was synthesized according to the following scheme 6. [Chemical 32]

In a 1 L eggplant-type flask, 25.4 g of compound (vi-1), 300 mL of acetonitrile, 48.0 g of di-tert-butyl dicarbonate (Boc ₂ O), and 1.22 g of N, N-dimethylformaldehyde were added. Aminopyridine was reacted at room temperature for 6 hours. After the reaction was completed, the reaction solution was concentrated to 100 mL, and then reprecipitated in 1 L of water, and the resulting precipitate was recovered by filtration and dried to obtain 40.9 g of compound (VI).

[Synthesis Example 1-7: Synthesis of Compound (VII)] Compound (VII) was synthesized according to the following scheme 7. [Chemical 33]

In a 1 L eggplant-shaped flask, 51.2 g of compound (vii-1), 500 mL of acetonitrile, 48.0 g of di-tert-butyl dicarbonate (Boc ₂ O), and 1.22 g of N, N-dimethyl Aminopyridine was reacted at room temperature for 6 hours. After the reaction was completed, the reaction solution was concentrated to 150 mL, and then reprecipitated in 1 L of water, and the resulting precipitate was recovered by filtration and dried to obtain 64.2 g of compound (VII).

[Synthesis Example 1-8: Synthesis of Compound (VIII)] Compound (VIII) was synthesized according to the following Scheme 8. [Chem 34]

4.54 g of 4-methacryloxybenzoic acid and 1.08 g of 1,4-diaminobenzene were suspended in 30 mL of dichloromethane, and the mixture was cooled in an ice bath. 5.76 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.488 g of N, N-dimethyl-4-aminopyridine were added thereto. . After stirring at room temperature for 6 hours, the suspended solid was filtered and the solid was washed with ethanol. This solid was dried to obtain 3.4 g of a compound (viii-1) with a purity of 99%. 3.0 g of compound (viii-1) was suspended in 30 mL of THF, and in this solution, 2.0 g of di-tert-butyl dicarbonate (Boc ₂ O) was dissolved in 30 mL of THF. To this solution was added 1.49 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring at room temperature for 3 hours, the solution was concentrated and the solid was dried to obtain 3.4 g of compound (VIII) with a purity of 99%.

[Synthesis Example 1-9: Synthesis of compound (C-1)] The compound (C-1) was synthesized according to the following scheme 9. [Chemical 35]

In a 500 mL eggplant-type flask equipped with a nitrogen introduction tube and a reflux tube, add 30.2 g of the compound (C-1a), 200 mL of thionyl chloride, and 0.1 mL of N, N-dimethylformamide, and reflux. 1 hour. After completion of the reaction, the viscous liquid obtained by concentrating and drying was recrystallized in cyclohexane, and then filtered and dried to obtain 27.1 g of a compound (C-1).

[Synthesis Example 1-10: Synthesis of Compound (ADBA1)] A compound (ADBA1) was synthesized according to the following scheme 13. [Chemical 36]

In a 1 L eggplant flask, add 28.6 g of compound (DA1), 300 mL of acetonitrile, 45.8 g of di-tert-butyl dicarbonate (Boc ₂ O), and 1.01 g of triethylamine at room temperature. Reaction for 6 hours. After the completion of the reaction, the reaction solution was concentrated to 100 mL, and then reprecipitated in 1 L of water. The resulting precipitate was recovered by filtration and dried to obtain 43.8 g of a compound (ADBA1).

[Synthesis Example 1-11: Synthesis of Compound (ADC1)] A compound (ADC1) was synthesized according to the following scheme 14. [Chemical 37]

In a 500 mL eggplant flask equipped with a nitrogen introduction tube and a reflux tube, add 27.0 g of the compound (DC1), 200 mL of thionyl chloride, and 0.1 mL of N, N-dimethylformamide, and reflux for 1 hour. . After the reaction was completed, the viscous liquid obtained by concentrating and drying was recrystallized with cyclohexane, filtered, and dried to obtain 27.6 g of a compound (ADC1).

[Synthesis Example 1-12: Synthesis of Compound (3-7)] Compound (3-7) was synthesized according to the following scheme 17. [Chemical 38]

· Synthesis of compound (3-7A) In a 1 L eggplant-type flask, 16.6 g of nitrophenethylamine, 200 mL of acetonitrile, 43.7 g of di-tert-butyl dicarbonate (Boc ₂ O), and 1.22 g of N, N-dimethylaminopyridine was reacted at room temperature for 6 hours. After completion of the reaction, the reaction solution was concentrated to 100 mL, and then reprecipitated in 1 L of water. The resulting precipitate was recovered by filtration and dried to obtain 24.0 g of a compound (3-7A). · Synthesis of compound (3-7C) In a 1 L three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 24.0 g of compound (3-7A), 17.3 g of compound (3-7B), and 500 mL of dichloride were added. Methane, refluxed for 20 hours. After the reaction was completed, the solution was concentrated under reduced pressure to 100 mL, and then eluted with an alumina column (developing solvent: hexane: ethyl acetate = 6: 4), and concentrated and dried to obtain 22.9 g of the compound (3- 7C). · Synthesis of compound (3-7) In a 2 L autoclave, 22.9 g of compound (3-7C), 200 mL of tetrahydrofuran, 200 mL of ethanol, and 1.15 g of 5% Pd / C were charged. Next, hydrogen gas was blown to 1.4 kg / cm ² , and then the reaction was carried out at room temperature for 20 hours. After the reaction was completed, the filtrate obtained by filtering through celite was concentrated under reduced pressure to 50 mL, and the obtained solution was reprecipitated in 1 L of water. The precipitate was recovered by filtration, washed with methanol, and then vacuum-dried to obtain 17.9 g of a compound (3-7).

<Synthesis of Polymer> [Synthesis Example 2-1: Synthesis of Polymer (P1)] 100 mol parts of pyromellitic dianhydride (PMDA) and 100 mol parts of a compound as a diamine (I) Dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours to obtain a solution containing 20% by weight of polyamic acid. A small amount of the obtained polyamic acid solution was added, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity measured was 92 mPa · s. The polyamidic acid obtained here was used as a polymer (P1).

[Synthesis Example 2-2 to Synthesis Example 2-23, Synthesis Example 2-27, and Synthesis Example 2-28] The types and amounts of the tetracarboxylic dianhydride and diamine used were changed as described in Table 1 below. Other than that, polyamino acids were synthesized separately in the same manner as in Synthesis Example 2-1. About Synthesis Example 2-2, Synthesis Example 2-5, Synthesis Example 2-6, Synthesis Example 2-8, Synthesis Example 2-10 to Synthesis Example 2-12, Synthesis Example 2-14 to Synthesis Example 2-18, Synthesis In Examples 2-20 to Synthesis Examples 2-23, the obtained polyamic acid was used as a polymer (P2), a polymer (P5), a polymer (P6), a polymer (P8), and a polymer (P10). To polymer (P12), polymer (P14) to polymer (P18), polymer (R2) to polymer (R5). In addition, about Synthesis Example 2-3, Synthesis Example 2-4, Synthesis Example 2-7, Synthesis Example 2-9, Synthesis Example 2-13, Synthesis Example 2-19, Synthesis Example 2-27, Synthesis Example 2-28 To the obtained polyfluorenic acid solution, pyridine and acetic anhydride were added to carry out chemical hydration. The reaction solution after the chemical imidization was concentrated and prepared using NMP so that the concentration became 10% by weight.

[Table 1]

In Table 1, the numerical value in () of the tetracarboxylic dianhydride represents a use ratio [mole part] to 100 mol parts in total of the tetracarboxylic dianhydride used in polymer synthesis. The numerical value in () of the diamine represents the use ratio [mole part] with respect to a total of 100 mole parts of the tetracarboxylic dianhydride used for polymer synthesis. The abbreviations of the acid anhydride and diamine in Table 1 respectively represent the following compounds. <Tetracarboxylic dianhydride> A-1: pyromellitic dianhydride A-2: 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride A-3: 2, 3, 5-tricarboxy ring Amylacetic dianhydride A-4: 1R, 2S, 4S, 5R-1,2,4,5-cyclohexanetetracarboxylic dianhydride A-5: p-phenylene bis (trimellitic acid monoester anhydride) ) <Diamine> D-1: p-phenylenediamine D-2: 4-aminophenyl-4'-aminobenzylamine D-3: N- (4-aminophenyl) -N- Phenylbenzene-1,4-diamine D-4: 4-aminophenyl-4'-aminobenzoate D-5: 3- (3,5-diaminobenzyloxy) Cholestane

[Synthesis Example 2-24: Synthesis of polymer (P19)] A polymer (P19) was synthesized according to the following scheme 10. [Chemical 39]

In a 100 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, add 4.55 g of compound (VI), 50 mL of tetrahydrofuran, and 0.2 mL of N, N-dimethylformamide, and cool in an ice bath at 5 ° C or lower. . Next, after adding 3.39 g of the compound (C-1), 2.84 g of N-ethyl-N, N-diisopropylamine was gradually added, and then the temperature was returned to room temperature, and polymerization was performed day and night. After the reaction was completed, 100 mL of cyclopentanone was added, and the solution was separated and washed three times with 100 mL of water. Then, 100 mL of N-methyl-2-pyrrolidone was added to the organic layer, and concentrated to 70 g, and then added again. 100 mL of N-methyl-2-pyrrolidone was then concentrated to 70 g to obtain an N-methyl-2-pyrrolidone solution of the polymer (P19) (solid content concentration: 10%). The weight average molecular weight of the polymer (P19) was 5,500.

[Synthesis Example 2-25: Synthesis of polymer (P20)] A polymer (P20) was synthesized according to the following scheme 11. [Chemical 40]

In a 100 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, 7.12 g of compound (VII), 70 mL of tetrahydrofuran, and 0.2 mL of N, N-dimethylformamide were added and cooled in an ice bath at 5 ° C or lower. . Next, after adding 3.25 g of the compound (A-6), 2.84 g of N-ethyl-N, N-diisopropylamine was slowly added, and then the temperature was returned to room temperature, and polymerization was performed throughout the day and night. After the reaction was completed, 140 mL of cyclopentanone was added, and the mixture was washed three times with 140 mL of water. Then, 140 mL of N-methyl-2-pyrrolidone was added to the organic layer. After concentrating to 92 g, it was added again. 140 mL of N-methyl-2-pyrrolidone was concentrated to 92 g to obtain an N-methyl-2-pyrrolidone solution of the polymer (P20) (solid content concentration: 10%). The weight average molecular weight of the polymer (P20) was 6,100.

[Synthesis Example 2-26: Synthesis of polymer (R6)] A polymer (R6) was synthesized according to the following scheme 12. [Chemical 41]

In a 200 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, put 2.54 g of compound (vi-1), 50 mL of chloroform, 50 mL of water, and 0.8 g of sodium hydroxide, and perform an ice bath at 5 ° C or lower. cool down. Next, 3.39 g of the compound (C-1) was added, and after vigorously stirring for 4 hours, a white precipitate was obtained. This precipitate was insoluble in tetrahydrofuran and N-methyl-2-pyrrolidone.

[Synthesis Example 2-29: Synthesis of polymer (AP3)] A polymer (AP3) was synthesized according to the following scheme 15. [Chemical 42]

In a 100 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube, and a thermometer, 4.87 g of the compound (ADBA1), 25 mL of tetrahydrofuran, and 4.8 g of sodium hydride were added, and the solution was cooled in an ice bath at 5 ° C or lower. Next, a solution prepared by dissolving 2.70 g of the compound (ADC1) in 25 mL of tetrahydrofuran was slowly added dropwise, and then returned to room temperature to perform day and night polymerization. After the reaction was completed, 100 mL of cyclopentanone was added, and the mixture was washed three times with 100 mL of water. Then, 100 mL of cyclopentanone was added to the organic layer and concentrated to 61 g. Then, 100 mL of cyclopentanone was added again, and then concentrated to 61 g, thereby obtaining a cyclopentanone solution (solid content concentration: 10%) of the polymer (AP3). The weight average molecular weight of the polymer (AP3) was 5,000.

[Synthesis Example 2-30: Synthesis of polymer (AP4)] A polymer (AP4) was synthesized according to the following scheme 16. [Chemical 43]

In a 500 mL three-necked flask equipped with an oxygen introduction tube and a thermometer, 60 mL of N, N-dimethylacetamide, 0.5 g of copper chloride, 20 mL of pyridine, and 7.24 g of compound (V) were charged. Then, 248 mL of oxygen was introduced and reacted at room temperature for 2 hours. After the reaction was completed, 100 mL of cyclopentanone was added, and the solution was separated and washed 3 times with 100 mL of water. Next, 72 g of cyclopentanone was added to the organic layer, and concentrated to 72 g by concentration under reduced pressure. 72 g of cyclopentanone was added again, and concentrated to 72 g, thereby obtaining cyclopentan of the polymer (AP4). Ketone solution (10% solids concentration). The weight average molecular weight of the polymer (AP4) was 14,000.

[Synthesis Example 2-31: Synthesis of polymer (P21)] 100 mol parts of 1R, 2S, 4S, 5R-1,2,4,5-cyclohexanetetracarboxylic acid as a tetracarboxylic dianhydride The dianhydride and 70 mol parts of the compound (I) and 30 mol parts of the compound (3-7) were dissolved in N-methyl-2-pyrrolidone (NMP) at room temperature. 6 The reaction was carried out for one hour, and a solution containing 20% by weight of polyamic acid was obtained. A small amount of the obtained polyamic acid solution was added, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by weight. The measured solution viscosity was 89 mPa · s. The polyamidic acid obtained here was used as a polymer (P21).

[Example 1] <Preparation of liquid crystal alignment agent> To the polymer (P1) obtained in Synthesis Example 2-1 as a polymer, NMP and butyl cellosolve (BC) as organic solvents were added to prepare The solvent composition was a solution of NMP: BC = 50: 50 (weight ratio) and solid content concentration of 5.0% by weight. This solution was filtered by using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

<Evaluation of storage stability> The prepared liquid crystal alignment agent was added to a sample bottle, and it was left in an oven at a temperature of 40 ° C for one week, and the change in viscosity (mPa · s) was measured. Using an E-type rotary viscometer, the viscosity was measured at 25 ° C. Observe the increase and decrease in viscosity after one week. When the viscosity is less than 5%, it is evaluated as "good (○)", and when it is 5% or more and less than 10%, it is evaluated as "stable (Δ)". ", When it is 10% or more, it is evaluated as" poor (×) "in storage stability. As a result, in this example, it was judged that the storage stability was "good".

<Manufacturing of a liquid crystal display element for friction alignment> As a substrate, a glass substrate having metal electrodes (electrode A and electrode B) of two systems containing chromium patterned in a comb-tooth shape on one side was coated with a spinner. The prepared liquid crystal alignment agent was pre-baked on a hot plate at 80 ° C for 1 minute, and then baked on a hot plate at 230 ° C for 10 minutes to form a coating film with a thickness of about 800 Å. The coated film surface was subjected to a rubbing process using a friction machine having a roll wound with a nylon cloth, with a roller revolution of 1,000 rpm, a moving speed of a platform of 25 mm / sec, and a gross press-in length of 0.4 mm. Gives liquid crystal alignment ability. Furthermore, this substrate was ultrasonically washed in ultrapure water for 1 minute, and dried in a 100 ° C dust-free oven for 10 minutes, thereby producing a substrate having a liquid crystal alignment film on the surface containing a comb-shaped chromium electrode. This substrate having a liquid crystal alignment film is referred to as "substrate A".

On the other hand, on the side of a glass substrate having a thickness of 1 mm that does not have an electrode, a coating film of a liquid crystal alignment agent is formed in the same manner as described above, and a rubbing treatment is performed, followed by washing and drying. A substrate for a liquid crystal alignment film. This substrate having a liquid crystal alignment film is referred to as "substrate B". Then, the outer edge of the surface of the substrate that has been subjected to the rubbing treatment with the liquid crystal alignment film is coated with an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm, and the rubbing direction of each liquid crystal alignment film is reversed. In a parallel manner, two substrates A and B are arranged to face each other through a gap, and the outer edge portions are brought into contact with each other to be crimped to harden the adhesive. Next, the nematic liquid crystal (Merck, MLC-2042) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive, thereby manufacturing an in-plane switching method. LCD cell.

<Evaluation of Afterimage Characteristics (Image Persistence Characteristics)> An in-plane switching method liquid crystal display element was manufactured using the same method as the above-mentioned "manufacturing of a liquid crystal display element for friction alignment". This in-plane switching method liquid crystal display element was placed in an environment of 25 ° C. and 1 atmosphere. No voltage was applied to electrode B, and a combined voltage of 3.5 V AC voltage and 5 V DC voltage was applied to electrode A for 2 hours. Then, an AC voltage of 4 V was immediately applied to both the electrode A and the electrode B. The time from the moment when the AC voltage of 4 V was applied to both electrodes was measured until the difference in light transmittance between the electrode A and the electrode B could no longer be confirmed visually. The case where this time is less than 100 seconds is evaluated as a "good (○)" afterimage characteristic, and the case where 100 seconds or more and less than 150 seconds is evaluated as a "after (Δ)" afterimage characteristic, and more than 150 seconds The afterimage characteristics were evaluated as "bad (×)". As a result, the evaluation was "good" in this example.

[Example 2 to Example 9, Example 27, and Comparative Example 2, Comparative Example 3, and Comparative Example 5] Except that the type and amount of the polymer used were as described in Table 2 below, and The liquid crystal alignment agent was prepared in the same manner as in Example 1. In addition, using the prepared liquid crystal alignment agent, evaluation of storage stability, production of a liquid crystal display element for rubbing alignment, and evaluation of afterimage characteristics were performed in the same manner as in Example 1. The results are shown in Table 2 below.

[Table 2]

In Table 2, the numerical value of the blending ratio of the polymer represents the blending ratio [part by weight] with respect to 100 parts by weight of the total of the polymer components used in the preparation of the liquid crystal alignment agent.

[Example 10 to Example 22, Example 28, Example 32, Example 33, Example 36, and Comparative Example 1 and Comparative Example 4] Except that the types and amounts of the polymers used were as shown in the table Except for the aspect described in 2, a liquid crystal alignment agent was prepared in the same manner as in Example 1 described above. In addition, using the prepared liquid crystal alignment agent, evaluation of storage stability, production of a liquid crystal display element for rubbing alignment, and evaluation of afterimage characteristics were performed in the same manner as in Example 1. The results are shown in Table 2 above.

<Phase separation evaluation> About the liquid crystal aligning agent which blended two polymers, the phase separation of polymers was evaluated. First, the same operation as in Example 1 was performed except that only one of the two polymers was used, thereby preparing two types of liquid crystal alignment agents having different kinds of polymers. Next, for the prepared liquid crystal alignment agent, a fired film was prepared to measure the surface contact angles of the film (reference contact angles A1, A2 [°]). In addition, for the prepared liquid crystal alignment agent, a calcined film was also prepared by the same operation, and the surface contact angle B [°] of the film was measured. When the polymer has good phase separation, the two polymers are separated into an upper layer and a lower layer, so the surface contact angle B of the sintered film containing the two polymers is close to the surface contact of one of the two polymers On the other hand, when the angle (A1 or A2) is not so good, the surface contact angle B is considered to be a value close to the middle of the two polymers. Therefore, when the surface contact angle B of the sintered film containing two kinds of polymers is close to any of the reference contact angles A1 and A2, the phase separation is considered to be good, and the surface contact angle B is brought into contact with the two reference points. When the difference Δθ of any of the angles A1 and A2 is less than 5%, the phase separation is evaluated as "good (○)", and when the difference is 5% or more and less than 10%, it is evaluated as "possible (Δ)" and 10% The above situation was evaluated as "bad (×)". The evaluation results of the examples are shown in Table 2. In addition, Δθ is a value represented by the following formula (2). Δθ [%] = (｜ BA ｜ / B) × 100 ... (2) (In the formula (2), A is any of the reference contact angles A1 and A2, and B is the alignment using a liquid crystal containing two polymers. Contact angle of the sintered film

[Example 23] <Preparation of liquid crystal alignment agent> A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the type and amount of the polymer to be used were as described in Table 2 above. . <Evaluation of Storage Stability> Using the prepared liquid crystal alignment agent, the storage stability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1. As a result, it was evaluated as "OK" in this example.

<Manufacturing of a liquid crystal display element for optical alignment (1)> A glass substrate having metal electrodes (electrode A and electrode B) of 2 systems containing chromium patterned in a comb-tooth shape on one side, and a pair of electrodes without electrodes The prepared liquid crystal alignment agent was applied to the surface of the glass substrate with a thickness of 0.1 μm using a spinner, dried on a hot plate at 80 ° C. for 1 minute, and dried in a 200 ° C. dust-free oven. A coating film was formed in 1 hour. A Hg-Xe lamp was used on the surface of the coating film, and polarized ultraviolet rays including bright lines of 254 nm were illuminated from the direction of the substrate normal to 10,000 J / m ² to form a liquid crystal alignment film. Next, for the pair of substrates subjected to the light irradiation treatment, a liquid crystal injection port remained at the edge of the surface on which the liquid crystal alignment film was formed, and an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was applied. The substrate was screen-printed and coated, and then the substrates were laminated and pressure-bonded so that the projection direction of the polarization axis on the substrate surface during light irradiation became antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, the liquid crystal injection port was filled with a nematic liquid crystal (Merck, MLC-7028) between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to eliminate the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 150 ° C. Next, polarizing plates are bonded to both outer surfaces of the substrate to produce an in-plane switching system liquid crystal display element.

<Evaluation of afterimage characteristics> An in-plane switching method liquid crystal display element was manufactured by the same method as the above-mentioned "manufacturing of a liquid crystal display element for optical alignment (1)", and the residual method was performed by the same method as in Example 1. Evaluation of image characteristics. As a result, it was difficult to generate an afterimage in this example, and the evaluation was “good”.

[Example 24 to Example 26] A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the types and amounts of the polymers used were as described in Table 2 above. In addition, using the prepared liquid crystal alignment agent, storage stability was evaluated in the same manner as in Example 1. A liquid crystal display element for light alignment was manufactured in the same manner as in Example 23 except that the liquid crystal alignment agent used was changed. The liquid crystal display element for light alignment was manufactured in the same manner as in Example 1. The evaluation of afterimage characteristics was performed in the same manner. In Examples 25 and 26 in which two polymers were blended to prepare a liquid crystal alignment agent, the phase separation of the two polymers was evaluated by the same method as in the <phase separation evaluation>. The results are shown in Table 2 above.

[Example 29, Example 30] <Preparation of liquid crystal alignment agent> The same manner as in Example 1 was performed except that the type and amount of the polymer to be used were as described in Table 2 above. A liquid crystal alignment agent is prepared. <Evaluation of Storage Stability> Using the prepared liquid crystal alignment agent, storage stability was evaluated in the same manner as in Example 1. As a result, both Example 29 and Example 30 were evaluated as "good."

<Manufacturing of a liquid crystal display element for photo-alignment (2)> A glass substrate having metal electrodes (electrode A and electrode B) of 2 systems containing chromium patterned in a comb-tooth shape on one side, and Opposite glass substrates were used as a pair of substrate surfaces, each of the prepared liquid crystal alignment agents was coated with a spinner so that the film thickness became 0.1 μm, and was fired on a hot plate at 80 ° C. for 1 minute. Next, a Hg-Xe lamp was used to irradiate polarized ultraviolet rays including bright lines of 254 nm from the direction of the substrate normal to 10,000 J / m ² of polarized light, and then dried in a 200 ° C dust-free oven for 1 hour to form a liquid crystal. Alignment film. Next, for the pair of substrates, a liquid crystal injection port remained at the edge of the surface where the liquid crystal alignment film was formed, and the epoxy resin adhesive to which alumina balls having a diameter of 5.5 μm were added was screen-printed and coated. The substrate was overlapped and crimped so that the projection direction of the polarization axis on the substrate surface during light irradiation was antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, the liquid crystal injection port was filled with a nematic liquid crystal (Merck, MLC-7028) between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to eliminate the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 150 ° C. Then, polarizing plates are bonded to both outer surfaces of the substrate to produce an in-plane switching system liquid crystal display element.

<Evaluation of afterimage characteristics> An in-plane switching method liquid crystal display element was manufactured by the same method as the above-mentioned "manufacturing of a liquid crystal display element for optical alignment (2)", and the residual method was performed by the same method as that of the first embodiment Evaluation of image characteristics. As a result, the evaluation was “good” in Example 29, and the evaluation was “OK” in Example 30. <Phase separation evaluation> Using the prepared liquid crystal alignment agent, the same operation as the above-mentioned <phase separation evaluation> was used to evaluate the phase separation of two polymers. As a result, both Example 29 and Example 30 were evaluated as "good."

As shown in Table 2, by using the polymer (P) that protects the amide bond, as a result, the afterimage characteristics are not impaired, and storage stability can be improved. In addition, when a polymer having a high fluorinated imidization rate (for example, a polymer having a fluorinated imidization rate of 90% or more) was used, good results were obtained with respect to storage stability. Furthermore, it can be seen that although a polymer having strong hydrogen bonding properties such as the polymer (P20) is not very good in storage stability, by introducing a protective group, the solubility in a solvent is improved, and storage stability can be improved. In addition, good results were obtained in the afterimage characteristics of the liquid crystal display element. The reason is presumably because the protective gene introduced into the polymer is detached from the heat, so that a highly-aligned structure is regenerated after post-baking. Regarding the phase separation of a system in which a plurality of polymers were blended, all of the examples were good. The reason is presumably because the hydrophobicity of the polymer (P) increases due to the effect of the introduction of the protective group, and a polarity difference occurs between the polymer (P) and the polymer having no protective group, so that the phase separation is improved. In addition, for the reason described above, even when a polymer having poor liquid crystal alignment such as the polymer (R1) and tends to have reduced afterimage characteristics of the liquid crystal display element, phase separation is caused, and the upper layer is biased. There is a film with high alignment, and the result is presumed to be a good result in the evaluation of afterimage characteristics.

[Example 31] <Preparation of liquid crystal alignment agent> To a solution containing the polymer (R5) obtained in Synthesis Example 2-23 as a polymer component, NMP and a butyl cellosolve (BC) as organic solvents were added. ), And based on 100 parts by weight of the polymer (R5), 20 parts by weight of the compound (VIII) synthesized in Synthesis Example 1-8 was added as an additive to make a solvent composition of NMP: BC = 50: 50 (weight Ratio), a solution with a solid content concentration of 6.0% by weight. This solution was filtered by using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

<Evaluation of printability> Using the liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), the prepared liquid crystal alignment agent was applied on a transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film. After heating (pre-baking) on a 80 ° C hot plate for 1 minute to remove the solvent, it is heated (post-baking) on a 200 ° C hot plate for 10 minutes to form a coating film with an average film thickness of 600 Å. This coating film was observed with a microscope with a magnification of 20 times, and the presence of uneven printing and pinholes was investigated. A case where neither printing unevenness nor pinholes were observed was evaluated as "good" printability, and a case where at least any one of printing unevenness and pinholes were slightly observed was evaluated as printability "may", and A case where at least one of a large number of uneven prints and pinholes was seen was evaluated as "poor" printability. In this example, neither printing unevenness nor pinholes were observed, and printability was "good".

<Manufacturing of a liquid crystal display element> A liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.) was used. One of the ITO electrodes was patterned into a slit shape as shown in FIG. The prepared liquid crystal alignment agent was applied to each electrode surface of a glass substrate, heated (pre-baked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C ) For 10 minutes, a coating film with an average film thickness of 600 Å was formed. This coating film was subjected to a rubbing treatment using a rubbing machine having a roll wound with a rayon cloth at a roll number of 400 rpm, a table moving speed of 3 cm / sec, and a gross press-in length of 0.1 mm. Then, ultrasonic washing was performed in ultrapure water for 1 minute, and then dried in a 100 ° C dust-free oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film. In addition, the rubbing treatment performed is a weak rubbing treatment performed for the purpose of controlling the collapse of the liquid crystal and performing the alignment division by a simple method. Next, for one of the pair of substrates, the outer edge of the surface having the liquid crystal alignment film is coated with an epoxy resin adhesive having alumina balls having a diameter of 5.5 μm, and then the liquid crystal alignment film faces are opposed to each other. In this method, a pair of substrates are overlapped and pressure-bonded to harden the adhesive. Next, a nematic liquid crystal (Merck, MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light-curing adhesive to manufacture a liquid crystal cell. For the obtained liquid crystal cell, a 10 V AC having a frequency of 60 Hz was applied between the electrodes, and the liquid crystal was driven with an ultraviolet irradiation device using a metal halide lamp as a light source at an irradiation amount of 10,000 J / m ² To irradiate ultraviolet rays. It should be noted that the exposure amount is a value measured using a light meter that measures at a wavelength of 365 nm.

<Evaluation of Afterimage Characteristics> The produced liquid crystal display element was left in an environment of 25 ° C. and 1 atmosphere, and no voltage was applied to the electrode B, and an AC voltage of 10 V was applied to the electrode A for 300 hours. Immediately after 300 hours, an AC voltage of 3 V was applied to both electrode A and electrode B, and the difference ΔT [%] in the light transmittance between the two electrodes was measured. At this time, the case where ΔT is less than 2% is evaluated as the afterimage characteristic “Good (○)”, the case where 2% or more and less than 4% is evaluated as the afterimage characteristic “OK (Δ)”, and the case where 4% or more is evaluated It was evaluated as "bad (×)" in afterimage characteristics. As a result, the evaluation was "good" in this example.

[Comparative Example 6 and Comparative Example 7] A liquid crystal alignment agent was prepared in the same manner as in Example 31 except that the types and amounts of the additives used were as described in Table 3 below. In addition, using the prepared liquid crystal alignment agent, evaluations of printability, production of a liquid crystal display element, and evaluation of afterimage characteristics were performed in the same manner as in Example 31. The results are shown in Table 3 below.

[table 3]

In Table 3, the numerical values of the blending ratio of the polymer and the additive represent the blending ratio [part by weight] with respect to 100 parts by weight of the total polymer component used in the preparation of the liquid crystal alignment agent. The abbreviations of the additives are as follows. Add-1: Compound represented by the following formula (Add-1) Add-2: Compound represented by the following formula (Add-2) [Chem. 44]

As shown in Table 3, in Example 31, by using a compound having a protective group introduced into the amido bond portion as a photopolymerizable compound, not only the afterimage characteristics of the liquid crystal display element can be maintained, but also the printability can be improved. On the other hand, in Comparative Example 6 in which the protective group was not introduced into the amido bond portion, the printability was "poor", and Comparative Example 7 without a nitrogen atom had worse after-image characteristics than the Examples.

[Example 34] <Preparation of liquid crystal alignment agent> To the polymer (AP3) obtained in Synthesis Example 2-29 as a polymer, NMP and butyl cellosolve (BC) as organic solvents were added to prepare The solvent composition was a solution of NMP: BC: cyclopentanone = 20: 50: 30 (weight ratio) and a solid content concentration of 5.0% by weight. This solution was filtered by using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent. <Evaluation of Storage Stability> Using the prepared liquid crystal alignment agent, the storage stability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1. As a result, in this example, the evaluation was "good" for storage stability.

<Manufacturing of a liquid crystal display element for optical alignment (3)> A glass substrate having metal electrodes (electrode A and electrode B) of 2 systems containing chromium patterned in a comb-tooth shape on one side, and a pair without electrodes The prepared liquid crystal alignment agent was applied to the surface of the glass substrate so that the film thickness became 0.1 μm, and dried in a dust-free oven at 200 ° C. for 1 hour to form a coating film. A Hg-Xe lamp was used on the surface of the coating film, and polarized ultraviolet rays including bright lines of 365 nm were irradiated with 5,000 J / m ² from the substrate normal direction to form a liquid crystal alignment film. Next, for the pair of substrates subjected to the light irradiation treatment, a liquid crystal injection port remained at the edge of the surface on which the liquid crystal alignment film was formed, and an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm was threaded. After the screen printing coating, the substrates were laminated and pressure-bonded so that the projection direction of the polarization axis on the substrate surface during light irradiation became antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, the liquid crystal injection port was filled with a nematic liquid crystal (Merck, MLC-7028) between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to eliminate the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 150 ° C. Next, polarizing plates are bonded to both outer surfaces of the substrate to produce an in-plane switching system liquid crystal display element.

<Evaluation of afterimage characteristics> A liquid crystal display element of the in-plane switching method was manufactured by the same method as the above-mentioned "Production of a liquid crystal display element for optical alignment (3)", and the residual method was performed by the same method as in Example 1. Evaluation of image characteristics. As a result, it was difficult to generate an afterimage in this example, and the evaluation was “good”.

[Example 35] A liquid crystal alignment agent was prepared in the same manner as in Example 34 except that the polymer (AP4) was used instead of the polymer (AP3). In addition, using the obtained liquid crystal alignment agent, evaluation was performed in the same manner as in Example 34. The results are shown in Table 4 below.

[Table 4]

As shown in Table 4, when a polymer having an azobenzene structure in the main chain was used as the polymer (P), the storage stability of the liquid crystal alignment agent was also good. In addition, good results were also obtained in the evaluation of the afterimage characteristics of the liquid crystal display element.

A, B‧‧‧ electrodes

ITO‧‧‧Indium Tin Oxide

FIG. 1 is an explanatory diagram showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film manufactured in an example and a comparative example.

Claims (9)

A liquid crystal alignment agent containing a compound (P) having a partial structure represented by the following formula (1), but excluding a polyamic acid and a polyamic acid having a partial structure represented by the following formula (8) Ester and polyimide,

In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond, and the protecting group is a third butoxycarbonyl group, a benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyl Yloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-oxylmethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethyl Oxycarbonyl or groups represented by the following formula (7-1) to formula (7-5),

In formula (7-1) to formula (7-5), Ar ¹ is a monovalent aromatic ring group having 6 to 10 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ is a monovalent organic group; "*" means a bond bonded to a nitrogen atom,

In formula (8), R ¹ and R ^{2 are} each independently a hydrogen atom, a C 1-4 alkyl group or a group represented by the following formula (9), at least one of which is a group represented by the formula (9);

In formula (9), A is a divalent group of a single bond or a hydrocarbon group having 1 to 4 carbon atoms. The liquid crystal alignment agent as described in item 1 of the patent application range, wherein the compound (P) is a polymer having a partial structure represented by the formula (1). The liquid crystal alignment agent as described in Item 2 of the patent application range, wherein the compound (P) is selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyamidoamine At least one. The liquid crystal alignment agent according to item 1 of the patent application scope, which contains at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyamidide, and The compound (P) as an additive. A liquid crystal alignment film formed using the liquid crystal alignment agent as described in any one of claims 1 to 4. A liquid crystal display element including the liquid crystal alignment film as described in item 5 of the patent application. A polymer that uses polyamic acid, polyamic acid ester, polyimide, or polyamidine as the main skeleton and has a partial structure represented by the following formula (1), but does not include the following formula (8) Polyamide acid, polyamic acid ester and polyimide of the partial structure shown,

In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond, and the protecting group is a third butoxycarbonyl group, a benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyl Yloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-oxylmethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethyl Oxycarbonyl or groups represented by the following formula (7-1) to formula (7-5),

In formula (7-1) to formula (7-5), Ar ¹ is a monovalent aromatic ring group having 6 to 10 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ is a monovalent organic group; "*" means a bond bonded to a nitrogen atom,

In formula (8), R ¹ and R ^{2 are} each independently a hydrogen atom, a C 1-4 alkyl group or a group represented by the following formula (9), at least one of which is a group represented by the formula (9);

In formula (9), A is a divalent group of a single bond or a hydrocarbon group having 1 to 4 carbon atoms. A diamine having a partial structure represented by the following formula (1), but excluding polyamic acid, polyamic acid ester, and polyimide having a partial structure represented by the following formula (8),

In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond, and the protecting group is a third butoxycarbonyl group, a benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyl Yloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-oxylmethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethyl Oxycarbonyl or groups represented by the following formula (7-1) to formula (7-5),

In formula (7-1) to formula (7-5), Ar ¹ is a monovalent aromatic ring group having 6 to 10 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ is a monovalent organic group; "*" means a bond bonded to a nitrogen atom,

In formula (8), R ¹ and R ^{2 are} each independently a hydrogen atom, a C 1-4 alkyl group or a group represented by the following formula (9), at least one of which is a group represented by the formula (9);

In formula (9), A is a divalent group of a single bond or a hydrocarbon group having 1 to 4 carbon atoms. A tetracarboxylic dianhydride having a partial structure represented by the following formula (1),

In formula (1), Y ¹ is a protecting group; "*" represents a bonding bond, and the protecting group is a third butoxycarbonyl group, a benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyl Yloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-oxylmethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethyl Oxycarbonyl or groups represented by the following formula (7-1) to formula (7-5),

In formula (7-1) to formula (7-5), Ar ¹ is a monovalent aromatic ring group having 6 to 10 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ is a monovalent organic group; "*" indicates a bond bonded to a nitrogen atom.