TWI694291B - Liquid crystal alignment agent, manufacturing method of liquid crystal element, liquid crystal alignment film, liquid crystal element and compound - Google Patents

Abstract

The liquid crystal alignment agent of this invention contains the following (A) component and (B) component. (A) Component: at least one selected from the group consisting of polymers of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, and monomer having a polymerizable unsaturated bond polymer. (B) Component: A photopolymerizable compound having at least any one of the following structures (C) and (D). (C) Structure: a portion that forms a weaker intermolecular force or a reversible covalent bond than a covalent bond between at least any one of the functional groups possessed by the (A) component and the (B) component structure. (D) Structure: A partial structure that forms a covalent bond by heating at least any one of the functional groups of the component (A) and the component (B).

Description

Liquid crystal alignment agent, manufacturing method of liquid crystal element, liquid crystal alignment film, liquid crystal element and compound

The invention relates to a liquid crystal alignment agent, a method for manufacturing a liquid crystal element, a liquid crystal alignment film, a liquid crystal element and a compound.

In the liquid crystal element, a multi-domain vertical alignment (MVA) type panel previously known as a vertical alignment mode forms a protrusion in the liquid crystal panel, thereby restricting the collapse direction of liquid crystal molecules, thereby realizing the viewing angle expand. However, according to this method, the lack of transmittance and contrast caused by the protrusions is unavoidable, and there is a disadvantage that the response speed of the liquid crystal molecules is relatively slow.

In recent years, in order to solve the problems of the MVA type panel as described above, a polymer stabilized alignment (Polymer Sustained Alignment, PSA) mode has been proposed (for example, refer to Patent Document 1). This PSA technique is a technique in which a component (photopolymerizable compound) polymerized by light irradiation is mixed into the liquid crystal layer of a liquid crystal cell, and the liquid crystal cell is irradiated with light while the liquid crystal molecules are tilted by voltage application. By this, the photopolymerizable compound is polymerized to control the molecular alignment of the liquid crystal molecules. However, when PSA technology is used to control the alignment of liquid crystal molecules, it is necessary to perform light irradiation with a relatively high irradiation amount. Therefore, in addition to the problem of decomposition of liquid crystal molecules, unreacted compounds that do not polymerize even after being irradiated with ultraviolet rays remain in the liquid crystal layer, and they may interact to cause uneven display, or voltage retention characteristics and long-term panel performance. Reliability decline.

In this regard, a technique for obtaining a liquid crystal element capable of imparting a desired pretilt angle characteristic to a coating film formed using a liquid crystal alignment agent with as little light irradiation amount as possible, and a liquid crystal is proposed The response speed of molecules to voltage changes is fast enough (for example, refer to Patent Document 2). This Patent Document 2 discloses that a liquid crystal alignment agent containing a polymer having a photopolymerizable group is used to form a liquid crystal alignment film on a substrate, and the substrate is used to form a liquid crystal cell, and the liquid crystal is applied with a voltage applied between the substrates. The cell is irradiated with light, thereby manufacturing a liquid crystal element.

In addition, in recent years, a liquid crystal cell manufacturing method that has been adopted along with the enlargement of the substrate has a liquid crystal drop method (One Drop Filling, ODF method). The ODF method is a method in which a required amount of liquid crystal is dropped at predetermined positions on a substrate on which a liquid crystal alignment film is formed, and is bonded to another substrate in a vacuum, and the liquid crystal is spread on the entire surface of the substrate Then, ultraviolet seal (ultraviolet, UV) is applied to the sealant used to seal the liquid crystal, thereby filling the entire surface of the panel with liquid crystal. This method is a technology that can greatly shorten the process time of the liquid crystal filling step compared to the vacuum injection method previously performed. In particular, this method is often used in the production of vertical alignment type liquid crystal display elements used in large liquid crystal display elements such as televisions. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2003-149647 [Patent Literature 2] Japanese Patent Laid-Open No. 2011-118358

[Problems to be solved by the invention]

The method for manufacturing a liquid crystal element using the ODF method has the advantages described above. On the other hand, display unevenness called "ODF unevenness" is likely to occur, which may affect display quality. In addition, with the high definition of liquid crystal panels in recent years, the requirements for display quality are becoming stricter, and new liquid crystal alignment agents are required, which can shorten the manufacturing process time of liquid crystal elements and accelerate the response speed of liquid crystal molecules to obtain Liquid crystal elements that hardly produce afterimages or uneven display.

The present invention has been made in view of the above circumstances, and one of the objects is to provide a liquid crystal alignment agent that can obtain a liquid crystal element with good afterimage characteristics and less ODF unevenness. [Technical means to solve the problem]

When a liquid crystal alignment agent containing a photopolymerizable compound as an additive is used to manufacture a liquid crystal element by the ODF method, as a cause of ODF unevenness, it is assumed that one of the reasons is listed as follows: when dropped on the alignment film When the liquid crystal is diffused, the photopolymerizable compound dissolves into the liquid crystal. Furthermore, it has been found that the inclusion of a photopolymerizable compound having a specific partial structure in the liquid crystal alignment agent can solve the above-mentioned problems and complete the present invention. Specifically, the following means are provided by the present invention.

[1] A liquid crystal alignment agent, containing the following components (A) and (B): (A) component: selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane And at least one polymer in the group consisting of polymers of monomers having polymerizable unsaturated bonds; (B) component: having at least one of the following structures (C) and (D) A photopolymerizable compound of a specific structure; (C) structure: at least any one of the functional groups possessed by the (A) component and the (B) component, more than a covalent bond A weak intermolecular force or a partial structure that forms a reversible covalent bond; (D) structure: at least any one of the (A) component and the (B) component by heating And part of the structure to form a covalent bond. [Effect of invention]

According to the liquid crystal aligning agent containing the said (A) component and (B) component, the liquid crystal element which has few afterimages and ODF unevenness and good display quality can be obtained.

Hereinafter, each component contained in the liquid crystal aligning agent of this invention, and other components arbitrarily mixed as needed are demonstrated.

<(A) component> The liquid crystal aligning agent of this invention contains the polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, and the monomer which has a polymerizable unsaturated bond At least one of the formed groups (hereinafter also referred to as "specific polymer"). [Polyamide] The polyamide of the present invention can be obtained by reacting tetracarboxylic dianhydride and a diamine compound.

(Tetracarboxylic dianhydride) Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. . As specific examples of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides include, for example, 1,2,3,4-butane tetracarboxylic dianhydride, etc.; and alicyclic tetracarboxylic dianhydrides include, for example. : 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-bi-side-oxytetrahydrofuran-3-yl)- 3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-bi-oxotetrahydrofuran-3-yl)-8-methyl- 3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6- Spiro ring-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-bi-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3. 0]Octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, cyclohexane Alkanetetracarboxylic dianhydride, etc.; examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)bisphthalic anhydride, etc.; It is possible to use the tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188. In addition, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

（式（E-1）中，X^I 及X^II 分別獨立地為單鍵、-O-、*-COO-或者*-OCO-（其中，“*”表示與X^I 的結合鍵），R^I 為碳數1～3的烷二基，R^II 為單鍵或碳數1～3的烷二基，a為0或1，b為0～2的整數，c為1～20的整數，d為0或1；其中，a及b不會同時成為0） 所表示的化合物等含配向性基的二胺：(Diamine compound) Examples of the diamine compound used in the synthesis of polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine-based organosiloxanes. As specific examples of these diamines, aliphatic diamines include, for example, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Etc.; alicyclic diamines, for example: 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), etc.; aromatic diamines, for example: dodecyloxy Diaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryloxydiaminobenzene, diaminobenzene Cholesteryl alkyl formate, cholesteryl diaminobenzoate, lanostyl diaminobenzoate, 3,6-bis(4-aminobenzyloxy)cholesterane, 3 ,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, following formula (E-1) [Chem 1]

(In formula (E-1), X ^I and X ^II are independently a single bond, -O-, *-COO- or *-OCO- (wherein "*" represents a bond with X ^I ), R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20, d is 0 or 1; wherein, a and b do not become 0 at the same time) Diamines containing aligning groups such as the compound represented by:

P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4 ,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, bis[2-(4-aminophenyl)ethyl]adipic acid, N,N -Bis(4-aminophenyl)methylamine, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, N,N'-bis(4- Aminophenyl)-benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl ) Hexafluoropropane, 4,4'-(phenylene diisopropyl) bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-amino Phenoxy) biphenyl and the like; diaminoorganosiloxanes include, for example, 1,3-bis(3-aminopropyl)-tetramethyldisilaxane, etc. In addition, Japanese patents can be used The diamine described in Japanese Patent Laid-Open No. 2010-97188.

（式（C-1）中，X⁹ 為單鍵、氧原子或碳數1～3的烷二基；m1及m2分別獨立地為0或1）As the diamine compound used in the synthesis of the polyamic acid, a diamine having a carboxyl group (hereinafter also referred to as "carboxyl-containing diamine") can be preferably used. By blending a polymer having a partial structure derived from a carboxyl group-containing diamine with the following (B) component, it is preferable in terms of improving the improvement effect of reducing the display unevenness of the liquid crystal display element. As the carboxyl group-containing diamine used in the synthesis, a diamine having an aromatic carboxylic acid structure having a structure in which a carboxyl group is bonded to an aromatic ring such as a benzene ring can be preferably used. Specifically, the compound represented by following formula (C-1) etc. are mentioned, for example. [Chem 2]

(In formula (C-1), X ⁹ is a single bond, an oxygen atom or a C1-C3 alkanediyl group; m1 and m2 are independently 0 or 1)

Specific examples of the compound represented by the formula (C-1) include, for example, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, and 2,5-diaminobenzoic acid , 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane- Monocarboxylic acids such as 3-carboxylic acid; 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid , 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-di Dicarboxylic acids such as aminodiphenylethane-3,3'-dicarboxylic acid and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid.

When synthesizing a polyamic acid, from the viewpoint of sufficiently obtaining the improvement effect of suppressing ODF unevenness caused by the use of the diamine, the carboxyl group-containing diamine is contained relative to the total amount of the diamine used in the synthesis. The use ratio of the amine is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more. In addition, the upper limit of the use ratio is not particularly limited, and from the viewpoint of the voltage retention rate, the use ratio of the carboxyl group-containing diamine is preferably set to the total amount of the diamine used in the synthesis. 90 mol% or less, more preferably 80 mol% or less. In addition, the carboxyl group-containing diamine may be used alone or two or more of them may be appropriately selected and used.

(Synthesis of Polyamic Acid) Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and the diamine compound as described above together with a molecular weight modifier if necessary. The use ratio of the tetracarboxylic dianhydride and the diamine compound supplied to the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine compound, and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 to 2 equivalents proportion. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, phenyl isocyanate, and isocyanate. Monoisocyanate compounds such as naphthyl cyanate. The use ratio of the molecular weight regulator is preferably 20 parts by mass or less relative to 100 parts by mass of the total amount of tetracarboxylic dianhydride and diamine compound used.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are preferably selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ- One or more of the group consisting of butyrolactone, tetramethylurea, hexamethylphosphoryltriamine, m-cresol, xylenol and halogenated phenol are used as solvents, or one or more of these solvents are used in combination with other organic solvents (Eg butyl cellosolve, diethylene glycol diethyl ether, etc.) mixture. The use amount (a) of the organic solvent is preferably such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1% to 50% by mass relative to the total amount of reaction solution (a+b). . In this way, 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 polyamic acid contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent.

[Polyamidate] The polyamic acid ester of the present invention can be obtained by the following method: for example, [I] a method of reacting the polyamic acid obtained by the synthesis reaction with an esterifying agent; [II] A method of reacting a tetracarboxylic acid diester and a diamine compound; and [III] A method of reacting a tetracarboxylic acid diester dihalide and a diamine compound. The polyamic acid ester contained in the liquid crystal alignment agent may have only the amide acid ester structure, or may be a partial esterified product in which the amide acid structure and the amide acid ester structure coexist. In addition, the reaction solution obtained by dissolving the polyamic acid ester may be directly provided to the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution may be separated and then provided to the preparation of the liquid crystal alignment agent.

[Polyimide] Polyimide can be obtained by, for example, dehydrating and ring-closing polyamic acid synthesized in the above-described manner, and subjecting it to imidization. The polyimide may be a complete imide compound obtained by dehydrating and ring-closing all the amidic acid structures of the polyamic acid as a precursor thereof, or may be dehydrating and ring-closing only a part of the amidic acid structure. A part of the imidate compound that coexists with the imidate structure and the imidate ring structure. The polyimide used in the reaction is preferably an imidate ratio of 20% to 99%, more preferably 30% to 90%. The imidate ratio is the sum of the number of amide acid structures of the polyimide and the number of amide imine ring structures, and expresses the ratio of the number of amide imine ring structures as a percentage. Here, a part of the imidate ring may be an imidate ring.

The dehydration and ring closure of the polyamic acid is preferably carried out 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, The method of heating as needed. Among them, the latter method is preferred. In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, for example, an anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The use amount of the dehydrating agent is preferably 0.01 mol to 20 mol relative to 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, tripicoline, lutidine, and triethylamine can be used. The use amount of the dehydration ring-closing catalyst 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 users in the synthesis of polyamide. The reaction temperature of the dehydration ring-closure reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hour to 120 hours. In this way, a reaction solution containing polyimide was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyimide can be separated and then provided to the preparation of the liquid crystal alignment agent. Polyimide can also be obtained by the imidization of polyimide.

The polyamic acid, polyamic acid ester, and polyimide obtained in the above-described manner are preferably solutions having a concentration of 10 mPa·s to 800 mPa·s when they are made into a solution with a concentration of 10% by mass. The viscosity is more preferably a solution viscosity of 15 mPa·s to 500 mPa·s. In addition, the solution viscosity (mPa·s) of polyamic acid, polyamic acid ester, and polyimide is a good solvent for using these polymers (such as γ-butyrolactone, N-methyl-2-pyrrolidone Etc.) to prepare a polymer solution with a concentration of 10% by mass, using an E-type viscometer to measure the value at 25°C.

Polystyrene-converted weight average molecular weight (Mw) of polyacrylic acid, polyamic acid ester and polyimide determined by gel permeation chromatography (GPC) is preferably 1,000 to 500,000 , More preferably from 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw and the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. By being within the molecular weight range as described above, good alignment and stability of the liquid crystal display element can be ensured.

[Polyorganosiloxane] The polyorganosiloxane of the present invention can be obtained by, for example, hydrolyzing and condensing a hydrolyzable silane compound. Examples of silane compounds used in the synthesis of polyorganosiloxanes include tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethyl Alkoxysilane compounds such as oxysilane; 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(3-cyclohexylamino) ) Nitrogen and sulfur-containing alkoxysilane compounds such as propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidyl Epoxy-containing silane compounds such as oxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; 3-(meth)acryloyloxy Propylpropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyl Unsaturated bond-containing alkoxysilane compounds such as triethoxysilane; trimethoxysilylpropyl succinic anhydride, etc. The hydrolyzable silane compound may be used alone or in combination of two or more. In addition, "(meth)acryloyloxy" includes "acryloyloxy" and "methacryloyloxy".

The hydrolysis/condensation reaction can be carried out by preferably reacting one or two or more of the silane compounds described above with water in the presence of a suitable catalyst and an organic solvent. During the reaction, the proportion of water used is preferably 1 mol to 30 mol relative to 1 mol of the silane compound (total amount). Examples of the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and the like, and can be appropriately set. For example, it is preferably 0.01 times to 3 times the molar amount relative to the total amount of the silane compound. Examples of the organic solvent used include hydrocarbons, ketones, esters, ethers, alcohols, etc. Among these organic solvents, it is preferable to use an insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 parts by mass to 10,000 parts by mass with respect to a total of 100 parts by mass of the silane compound used in the reaction.

The hydrolysis/condensation reaction is preferably carried out by heating with an oil bath or the like. At this time, the heating temperature is preferably set to 130° C. or lower, and the heating time is preferably set to 0.5 to 12 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is dried with a desiccant as necessary, and then the solvent is removed, thereby obtaining the target polyorganosiloxane. In addition, the synthesis method of polyorganosiloxane is not limited to the above-mentioned hydrolysis and condensation reaction, and for example, it can be performed by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

The polyorganosiloxane as the component (A) may be a polyorganosiloxane having a liquid crystal alignment group on the side chain (hereinafter, also referred to as "alignment group-containing polysiloxane"). The method for synthesizing the aligning group-containing polysiloxane is not particularly limited, and the following methods may be mentioned: using at least a part of the raw material to synthesize a polysiloxane having an epoxy group on the side chain using an epoxy-containing silane compound Organosiloxane (hereinafter, also referred to as "epoxy group-containing polysiloxane"), in turn, reacts epoxy group-containing polysiloxane with a carboxylic acid having a liquid crystal alignment group. This method is simple and is preferable in that it can increase the introduction rate of the liquid crystal alignment group. In addition to this, it is also possible to synthesize the alignment group-containing polysiloxane by the reaction of including a hydrolyzable silane compound having a liquid crystal alignment group in the monomer. Regarding the polyorganosiloxane as the component (A), the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably in the range of 100 to 50,000, more preferably in the range of 200 to 10,000 Inside.

[Polymer of a monomer having a polymerizable unsaturated bond] In a polymer of a monomer having a polymerizable unsaturated bond (hereinafter, also referred to as "polymer (PAc)"), the polymerizability of the monomer does not Examples of the saturated bond include (meth)acryloyl, vinyl, styryl, maleimide, and the like. Specific examples of the monomer having a polymerizable unsaturated bond include, for example, (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid. Saturated carboxylic acid, alkyl (meth)acrylate, cycloalkyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid Trimethoxysilylpropyl ester, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic compounds such as unsaturated carboxylic acid esters such as 3,4-epoxybutyl ester, acrylic acid 4-hydroxybutyl glycidyl ether, and unsaturated polycarboxylic acid anhydrides such as maleic anhydride; styrene, methyl Aromatic vinyl compounds such as styrene and divinylbenzene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; N-methyl maletene Compounds containing maleimide group such as amide imine, N-cyclohexyl maleimide diimide, N-phenyl maleimide diimide, etc. In addition, the monomer having a polymerizable unsaturated bond may be used alone or in combination of two or more.

From the viewpoint of transparency, material strength, and the like, among the polymers, the polymer (PAc) is preferably a polymer containing a monomer of a (meth)acrylic compound. When synthesizing the polymer (PAc), the use ratio of the (meth)acrylic compound relative to the total amount of monomers used in the synthesis is preferably 50 mol% or more, more preferably 60 mol% Above, it is particularly preferable to set it to 70 mol% or more.

The polymer (PAc) can be obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator, for example. The polymerization initiator used is preferably, for example: 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used in the reaction. The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. Diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are preferred. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 hour to 36 hours. The use amount (a) of the organic solvent is preferably set to an amount of 0.1% by mass to 60% by mass relative to the total amount (a+b) of the reaction solution.

The polymer (PAc) as the component (A) may be a polymer having a liquid crystal alignment group on the side chain (hereinafter, also referred to as "alignment group-containing polymer (PAc)"). The method for synthesizing the aligning group-containing polymer (PAc) is not particularly limited. For example, the following methods may be mentioned: using at least a part of the raw material to synthesize a polymer having an epoxy group on the side chain using an epoxy group-containing compound And then react it with a carboxylic acid having a liquid crystal alignment group. Regarding the polymer (PAc), the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and particularly preferably 1,000 to 50,000.

Among them, the component (A) preferably includes at least one selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester. By the carboxyl group (equivalent to the functional group which (A) component has) which these polymers have, the interaction with (B) component improves. The specific polymer contained in the liquid crystal alignment agent may be used alone or in combination of two or more. (A) Preferred embodiments of the component include: <1> (A) The component is at least one embodiment selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester; <2> (A) The component is at least one selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester and an embodiment of polyorganosiloxane; <3> (A) The component is at least one selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester, the embodiment of the polymer (PAc), and the like.

<(B) component> The liquid crystal aligning agent of this invention contains not only (A) component, but also the photopolymerizable compound which has a specific structure as at least any one of the following (C) structure and the following (D) structure ( Hereinafter also referred to as "compound (B)"). In addition, the "photopolymerizable compound" in this specification means a compound having at least one photopolymerizable group. (C) Structure: In at least any one of the functional groups possessed by the (A) component and the (B) component, an intermolecular force weaker than the covalent bond is generated or a reversible covalent bond is formed Part of the structure. (D) Structure: In at least any one of the components (A) and (B), a partial structure in which a covalent bond is formed by heating.

（式（4）中，R¹ 為氧原子、硫原子或-NH-；X¹ ～X³ 分別獨立地為氫原子、鹵素原子或一價有機基；其中，在R¹ 為氧原子的情況下，X³ 也可以與其他基團鍵結而與-CO-R¹ -一起形成環；“*”表示結合鍵）The photopolymerizable group included in the compound (B) may be any functional group that can be polymerized by light irradiation, and examples thereof include a group having a polymerizable carbon-carbon unsaturated bond. Specific examples of these groups include, for example, (meth)acryloyl, vinyl, styryl, maleimide, and the like. The number of photopolymerizable groups possessed by the compound (B) is not particularly limited, and may be one or plural. From the viewpoint of appropriately controlling the pretilt angle of the coating film and accelerating the response speed of the liquid crystal molecules, it is preferably 2 or more, and more preferably 2 to 4. From the viewpoint of sufficiently increasing the alignment restricting force in the alignment film to reduce the afterimage, the compound (B) is preferably a compound having a group represented by the following formula (4) as a photopolymerizable group, more preferably It is a compound having two or more groups represented by the following formula (4). [Chemical 3]

(In formula (4), R ¹ is an oxygen atom, a sulfur atom, or -NH-; X ¹ to X ³ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group; where R ¹ is an oxygen atom Next, X ³ may also be bonded to other groups to form a ring with -CO-R ¹ -; "*" indicates a bonding bond)

（式（4-1）中，R¹ 為氧原子、硫原子或-NH-；X⁷ 為氫原子、甲基或全氟甲基）Examples of the monovalent organic groups of X ¹ to X ³ in the formula (4) include monovalent chain hydrocarbon groups having 1 to 12 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and 6 carbon atoms. Monovalent aromatic hydrocarbon groups of ~12, etc. The hydrogen atoms contained in these hydrocarbon groups may be substituted with halogen atoms or the like. X ¹ and X ^{2 are} preferably hydrogen atoms, and X ^{3 is} preferably a hydrogen atom, a fluorine atom, a C 1-6 alkyl group, a C 1-6 fluoroalkyl group, or a C 6-12 monovalent aromatic Ring base. Specific examples when X ³ is an aromatic ring group include, for example, phenyl, tolyl, and the like. Preferred specific examples of the partial structure represented by the formula (4) include the structures represented by the following formula (4-1) and formula (4-2). [Chemical 4]

(In formula (4-1), R ¹ is an oxygen atom, a sulfur atom, or -NH-; X ⁷ is a hydrogen atom, a methyl group, or a perfluoromethyl group)

（式（1）中，X⁴ 為氧原子或硫原子，R² 為氧原子、硫原子、烷二基、芳香環基、伸環己基、或者-NR³² -（R³² 為氫原子或保護基），R³⁰ 為氫原子或保護基；其中，在R² 為芳香環基或伸環己基的情況下，R³⁰ 為保護基；式（2）中，X⁵ 為二價烴基或-NR³³ -（R³³ 為氫原子或保護基）；“*”表示結合鍵）The specific structure is not particularly limited as long as it exhibits the above-mentioned characteristics, and can be appropriately selected according to the functional group possessed by the component (A). Here, the "intermolecular force weaker than the covalent bond" of the (C) structure refers to, for example, ion-dipole interaction, dipole-dipole interaction, hydrogen bond, coordination bond, van der Waals Electromagnetic force such as force that acts between molecules. (C) The structure includes, for example, a partial structure represented by the following formula (1), a partial structure represented by the following formula (2), a partial structure represented by the following formula (3), a tertiary amine structure, and Nitrogen heterocyclic structure, -NR ³¹ X ¹⁰ , -NHX ¹⁰ (wherein R ³¹ is a monovalent hydrocarbon group, X ¹⁰ is a protecting group), hydroxyl group, carboxyl group, -NH ₂ , -NHR ⁴¹ (R ⁴¹ is carbon number 1～ 6 monovalent hydrocarbon group), thiol group, phosphate group, etc. Among them, the structure (C) is preferably selected from a partial structure represented by the following formula (1), a partial structure represented by the following formula (2), a partial structure represented by the following formula (3), and a tertiary amine At least one of the group consisting of structure, nitrogen-containing heterocyclic structure, and -NR ³¹ X ¹⁰ . [Chem 5]

(In formula (1), X ⁴ is an oxygen atom or a sulfur atom, R ² is an oxygen atom, a sulfur atom, an alkanediyl group, an aromatic ring group, a cyclohexyl group, or -NR ^32- (R ³² is a hydrogen atom or a protection Group), R ³⁰ is a hydrogen atom or a protecting group; where R ² is an aromatic ring group or a cyclohexyl group, R ³⁰ is a protecting group; in formula (2), X ⁵ is a divalent hydrocarbon group or -NR ^33- (R ³³ is a hydrogen atom or a protecting group); "*" indicates a bond)

（式（8-1）～式（8-5）中，Ar¹¹ 為碳數6～10的一價芳香環基，R²¹ 為碳數1～12的烷基，R²³ 為亞甲基或伸乙基；“*”表示鍵結於氮原子上的結合鍵）In the above formula (1), the alkanediyl group of R ² may be exemplified by methylene, ethylidene, propanediyl, butanediyl, pentaneyl, etc. These groups may be linear or may be linear It is branched. Examples of the aromatic ring group include phenylene, biphenylene, and naphthyl, and may have a substituent in the ring portion. Examples of the substituent include alkyl groups, alkoxy groups, and halogen atoms. The protecting group for R ³⁰ and R ³² is preferably a group that is detached by heat, and examples thereof include a carbamate-based protecting group, an amide-based protecting group, an amide-based protecting group, and a sulfonamide-based protecting group. Group, groups represented by the following formula (8-1) to formula (8-5), etc., respectively. Among them, the third butoxycarbonyl group is preferable in terms of high thermal detachability or in terms of reducing the residual amount of the deprotected portion in the film. [化6]

(In formula (8-1) to formula (8-5), Ar ¹¹ is a monovalent aromatic ring group having 6 to 10 carbon atoms, R ²¹ is an alkyl group having 1 to 12 carbon atoms, and R ²³ is a methylene group or Ethylene; "*" means a bond bonded to a nitrogen atom)

In the formula (1), in terms of a high improvement effect of suppressing ODF unevenness, R ^{2 is} preferably an oxygen atom, a sulfur atom, an alkanediyl group or -NR ³² -, more preferably -NR ³² -, Particularly preferred is -NH-. From the standpoint of suppressing ODF unevenness, X ^{4 is} preferably a sulfur atom, and from the standpoint of ease of synthesis and cost of the compound, an oxygen atom is preferred. R ^{30 is} preferably a hydrogen atom. In the formula (2), the divalent hydrocarbon group of X ⁵ may include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Regarding the protecting group of R ³³ , examples of applying the protecting groups of R ³⁰ and R ³² and description of preferred specific examples. R ^{33 is} preferably a hydrogen atom. In addition, the nitrogen atom of "-C=N-" in formula (2) may be bonded to a monovalent group such as a hydrogen atom or an alkyl group, or may be bonded to X ⁵ to form a ring structure.

（式中，“*”表示結合鍵）As a preferable specific example of the partial structure represented by the formula (1), for example, the structures represented by the following formula (1-1) and formula (1-2), etc., can be cited as the formula (2) Preferred specific examples of the partial structure shown include, for example, structures represented by the following formula (2-1) and formula (2-2), respectively. [化7]

(In the formula, "*" represents the bond)

（式（N-1）中，R⁶ 為經取代或未經取代的一價烴基；“*”為鍵結於烴基上的結合鍵）The tertiary amine structure of (C) is a structure in which three hydrocarbon groups are directly bonded to the nitrogen atom, and is represented by the following formula (N-1), for example. [Chem 8]

(In formula (N-1), R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group; "*" is a bonding bond bonded to the hydrocarbon group)

In the formula (N-1), the monovalent hydrocarbon group of R ⁶ preferably has 1 to 10 carbon atoms, and specific examples include linear or branched groups such as methyl, ethyl, propyl, and butyl. Alkyl groups; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl; aralkyl groups such as benzyl. Examples of the substituent that R ⁶ may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group, a group represented by the following formula (4), and the like. R ^{6 is} preferably a C 1-5 alkyl group, a cyclohexyl group, a phenyl group or a benzyl group, and in terms of a high improvement effect of suppressing ODF unevenness, a C 1 to C 5 alkyl group or a ring is more preferred Hexyl or benzyl. Examples of the hydrocarbon group to which "*" in the formula (N-1) is bonded include alkanediyl group, cyclohexyl group, and phenylene group.

Examples of the nitrogen-containing heterocyclic structure of (C) include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, 1H-pyrrolo[2,3 -b]pyridine, purine, quinoline, isoquinoline, naphthyridine, phenazine, quinoxaline, phthalazine, triazine, oxazole, acridine, piperidine, piperazine, pyrrolidine and hexamethylene A nitrogen-containing heterocycle such as an amine, or a structure in which a substituent is introduced into the nitrogen-containing heterocycle. Here, the substituents possessed by the nitrogen-containing heterocyclic ring include, for example, C 1-5 alkyl groups, alkoxy groups, and the like. Wherein, the nitrogen-containing heterocycle is preferably selected from the group consisting of pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, imidazole, 1H-pyrrolo[2,3-b]pyridine and acridine At least one. From the viewpoint of response speed, the nitrogen-containing heterocyclic structure is preferably in the main chain of the compound (B). In "-NR ³¹ X ¹⁰ ", the monovalent hydrocarbon group of R ³¹ is preferably an alkyl group having 1 to 5 carbon atoms. Regarding X ¹⁰ , examples of applying the protecting groups of R ³⁰ and R ³² and explanations of preferred specific examples.

(D) Examples of the structure include epoxy groups (including oxetanyl and oxetanyl groups), isocyanate groups, blocked isocyanate groups, -NHX ¹⁰ (X ¹⁰ is a protecting group), hydroxyl group, carboxyl group,- NH ₂ , thiol group, etc. The block isocyanate group of (D) is not particularly limited as long as the isocyanate group is regenerated by deprotection by heat. The blocking agent that blocks the isocyanate group is not particularly limited, and examples thereof include alcohol-based compounds, phenol-based compounds, active methylene-based compounds, thiol-based compounds, amide-based compounds, amide-based compounds, Imidazole compound, pyrazole compound, urea compound, oxime compound, amine compound, imine compound, pyridine compound, etc. Among them, the structure (D) is preferably at least one selected from the group consisting of epoxy groups, isocyanate groups and blocked isocyanate groups, more preferably selected from the group consisting of isocyanate groups and blocked isocyanate groups At least one.

Among the partial structures, the specific structure possessed by the compound (B) is preferably selected from the partial structure represented by the formula (1), the partial structure represented by the formula (2), and the formula (3) At least one of the group consisting of the represented partial structure, tertiary amine structure, nitrogen-containing heterocyclic structure, -NR ³¹ X ¹⁰ , epoxy group, isocyanate group, and block isocyanate group. In terms of a high effect of improving the response speed of liquid crystal molecules, the structure (C) is preferable. Specifically, it is preferably selected from the partial structure represented by the formula (1), the partial structure represented by the formula (2), the partial structure represented by the formula (3), the tertiary amine structure, At least one of the nitrogen-containing heterocyclic structure and the group consisting of -NR ³¹ X ¹⁰ is preferably selected from the group consisting of the partial structure represented by the formula (2), the tertiary amine structure, and the nitrogen-containing heterocyclic structure At least one of the groups.

（式（6）中，Ar³ 及Ar⁴ 分別獨立地為1,4-伸苯基或1,4-伸環己基，X⁸ 為單鍵或-COO-；n2為1或2；當n2=2時，Ar⁴ 、X⁸ 分別獨立地具有所述定義；“*”表示結合鍵）From the viewpoint of improving the affinity with the liquid crystal and improving the response speed of the liquid crystal molecule, the compound (B) preferably has a partial structure represented by the following formula (6) in the molecule. [化9]

(In formula (6), Ar ³ and Ar ⁴ are independently 1,4-phenylene or 1,4-cyclohexyl, X ⁸ is a single bond or -COO-; n2 is 1 or 2; when n2 =2, Ar ⁴ and X ⁸ independently have the above definition; "*" indicates a bonding bond)

（式中，“*”表示結合鍵）Specific examples of the partial structure represented by the formula (6) include, for example, 4,4′-biphenylene, 4,4′-biscyclohexyl, and the following formula (6-1) to formula (6-4) Groups represented respectively. [化10]

(In the formula, "*" represents the bond)

（式（5）中，X⁶ 為氫原子、氟原子、碳數1～6的烷基、碳數1～6的氟烷基或碳數6～12的一價芳香族基，R³ 為氧原子、硫原子或-NH-，Ar¹ 及Ar² 分別獨立地為1,4-伸苯基、1,4-伸環己基、哌啶-1,4-二基、哌啶-2,5-二基、哌嗪-1,4-二基、哌嗪-2,5-二基、嘧啶-2,5-二基、噠嗪-3,6-二基、吡嗪-2,5-二基、吡啶-2,5-二基、伸萘基、四氫萘二基、或者十氫萘二基，也可以在環部分具有取代基；R⁴ 為單鍵、酯鍵、醯胺鍵、醚鍵、或者-CO-NR³⁴ -（R³⁴ 為保護基），R⁵ 為酯鍵、醯胺鍵、醚鍵、或者-CO-NR³⁵ -（R³⁵ 為保護基）；n1為0～2的整數；當n1=2時，R⁴ 、Ar² 分別獨立地具有所述定義；“*”表示結合鍵）From the viewpoint of improving the affinity with the liquid crystal, the compound (B) is preferably a compound having a partial structure represented by the following formula (5). [Chem 11]

(In formula (5), X ⁶ is a hydrogen atom, a fluorine atom, a C 1-6 alkyl group, a C 1-6 fluoroalkyl group, or a C 6-12 monovalent aromatic group, and R ³ is Oxygen atom, sulfur atom or -NH-, Ar ¹ and Ar ² are independently 1,4-phenylene, 1,4-cyclohexyl, piperidine-1,4-diyl, piperidine-2, 5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyrazine-2,5 -Diyl, pyridine-2,5-diyl, naphthyl, tetrahydronaphthalenediyl, or decahydronaphthalenediyl, may also have a substituent in the ring portion; R ⁴ is a single bond, ester bond, amide Bond, ether bond, or -CO-NR ^34- (R ³⁴ is a protecting group), R ⁵ is an ester bond, an amide bond, an ether bond, or -CO-NR ^35- (R ³⁵ is a protecting group); n1 is An integer from 0 to 2; when n1=2, R ⁴ and Ar ² independently have the above definition; “*” represents a bonding bond)

In formula (5), X ^{6 is} preferably a hydrogen atom, a fluorine atom, a methyl group or a fluoromethyl group, and more preferably a hydrogen atom or a methyl group. Examples of the substituent that the ring of Ar ¹ and Ar ² may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group, a group represented by the above formula (4), and the like. Ar ¹ and Ar ^{2 are} preferably 1,4-phenylene, 1,4-cyclohexyl, naphthyl, tetrahydronaphthalenediyl, or decahydronaphthalenediyl, more preferably 1,4-phenylene Base or 1,4-cyclohexyl. A substituent may be introduced into the ring portion of 1,4-phenylene and 1,4-cyclohexyl, but it is preferably unsubstituted. In addition, at least one of Ar ¹ and Ar ² is piperidine-1,4-diyl, piperidine-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5 -In the case of diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyrazine-2,5-diyl or pyridine-2,5-diyl, it has the formula ( 5) The compound (B) corresponds to a compound having a nitrogen-containing heterocyclic structure as the specific structure. The protecting groups of R ³⁴ and R ³⁵ can be exemplified by the protecting groups of R ³⁰ and R ³² and the description of preferred specific examples. In terms of improving the affinity with the liquid crystal, R ⁴ and R ^{5 are} preferably single bonds or ester bonds. In addition, the partial structure represented by the formula (6) may be introduced into the compound (B) as the group "-Ar ¹ -(R ⁴ -Ar ² ) _n1 -" in the formula (5), or It can be introduced into the compound (B) separately from this group. The former is preferred.

（式（D-1）中，Y¹ 為包含選自由所述式（1）所表示的部分結構、所述式（2）所表示的部分結構、所述式（3）所表示的部分結構、三級胺結構、含氮雜環結構以及-NR³¹ X¹⁰ 所組成的組群中的至少一種的二價基；R⁷ 為單鍵、酯鍵、醯胺鍵、醚鍵、或者-CO-NR³⁶ -（R³⁶ 為保護基）；R⁸ 為單鍵、烷二基、伸苯基、伸環己基、或者所述式（6）所表示的二價基；X⁶ 、R³ 、Ar¹ 、Ar² 、R⁴ 、R⁵ 及n1分別與所述式（5）為相同含義；多個X⁶ 及多個R³ 獨立地具有所述定義）Preferable specific examples of the compound (B) include, for example, compounds represented by the following formula (D-1). [化12]

(In formula (D-1), Y ¹ is selected from the partial structure represented by the formula (1), the partial structure represented by the formula (2), and the partial structure represented by the formula (3). , Tertiary amine structure, nitrogen-containing heterocyclic structure and at least one divalent group in the group consisting of -NR ³¹ X ¹⁰ ; R ⁷ is a single bond, ester bond, amide bond, ether bond, or -CO -NR ^36- (R ³⁶ is a protecting group); R ⁸ is a single bond, alkanediyl, phenylene, cyclohexyl, or the divalent group represented by the formula (6); X ⁶ , R ³ , Ar ¹ , Ar ² , R ⁴ , R ⁵ and n1 have the same meanings as the above formula (5); multiple X ⁶ and multiple R ³ independently have the above definition)

[化14]

[化15]

[化16]

[化17]

（式（DM-50）及式（DM-51）中，R¹¹ 為氫原子或甲基，R¹² 及R¹³ 分別獨立地為二價烴基；其中，式中的多個R¹¹ 可相同，也可以不同，多個R¹³ 可相同，也可以不同）Specific examples of the compound (B) include, for example, compounds represented by the following formula (DM-1) to formula (DM-79). In addition, the compound (B) may be used alone or in combination of two or more. [Chem 13]

[化14]

[化15]

[Chem 16]

[化17]

(In formulas (DM-50) and (DM-51), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² and R ¹³ are each independently a divalent hydrocarbon group; wherein, multiple R ¹¹ in the formula may be the same, It can also be different, multiple R ¹³ can be the same or different)

[化19]

[化20]

（式（DM-66）～式（DM-71）中，n為1～10的整數）[Chemical 18]

[Chem 19]

[化20]

(In formula (DM-66) to formula (DM-71), n is an integer of 1 to 10)

The compound (B) can be synthesized by appropriately combining ordinary methods of organic chemistry. For example, the polyfunctional (meth)acrylate compound having the specific structure may be exemplified by synthesizing a carboxylic acid having a partial structure represented by the formula (5), and then proceeding with the diol having the specific structure After the reaction, a method of reacting with unsaturated carboxylic acid such as (meth)acrylic acid; synthesizing a multifunctional (meth)acrylate compound having a partial structure represented by the formula (5) and a hydroxyl group, and then making it have A method of reacting the carboxylic acid of the specific structure; a method of reacting a benzoyl group-containing compound having the partial structure represented by the formula (5) with a polyol having the specific structure, etc. However, the synthesis method of the compound (B) is not limited to these methods.

In addition, the reason for obtaining the improvement effect of the afterimage characteristics and ODF unevenness by using the liquid crystal alignment agent containing the compound (B) is not certain, and one of the reasons is speculated that the specific structure possessed by the compound (B), The form of the bond between the compound (B) or between the specific polymer and the compound (B) changes with heat. For example, it is presumed that the photopolymerizable compound having a partial structure that forms a weaker intermolecular force than a covalent bond with a specific polymer and the like after the liquid crystal is dropped (for example, 80°C or less, preferably a room temperature) Temperature), intermolecular interaction (hydrogen bond or coordination bond) between specific polymer and compound (B), or between compound (B), to suppress the elution of compound (B) into the liquid crystal, another On the other hand, due to the heating during annealing after the construction of the liquid crystal cell, the intermolecular interaction is weakened. In addition, the (C) structure in this case is preferably not to form a covalent bond when heated. It is also speculated that the photopolymerizable compound having the partial structure represented by the formula (3) is obtained by the Diels-Alder reaction between the compound (B) at the temperature after the liquid crystal is dropped Reversible covalent bonds are formed. On the other hand, the covalent bonds are cut by heating during the annealing after the construction of the liquid crystal cell. It is presumed that the change in the bonding morphology suppresses the display unevenness caused by the elution of the compound (B) into the liquid crystal, and the response speed of the liquid crystal molecules increases. However, the above is speculation and is not limited to the present invention.

The content ratio of the compound (B) is preferably 1 part by mass or more, and more preferably 5 parts by mass relative to 100 parts by mass of the specific polymer as the component (A) contained in the liquid crystal alignment agent. Above, it is particularly preferably set to 10 parts by mass or more. If the content ratio of the compound (B) is less than 1 part by mass, there is a tendency that the response speed of the liquid crystal molecules in the liquid crystal display element becomes slow, which tends to cause afterimages. In addition, from the viewpoint of suppressing the occurrence of ODF unevenness caused by excessive addition of the photopolymerizable compound, it is preferable to set the content ratio of the compound (B) to 60 with respect to a total of 100 parts by mass of the specific polymer. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

<Other components> The liquid crystal aligning agent of this invention contains the said (A) component and (B) component, and may contain other components as needed. Examples of the other components include polymers other than the component (A), compounds having at least one epoxy group in the molecule and not having a photopolymerizable group, functional silane compounds, and light that does not have the specific structure Polymerizable compounds, compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, light sensitizers, etc. The blending ratio of these other components can be appropriately selected within a range that does not impair the effects of the present invention.

<Solvent> The liquid crystal alignment agent of the present invention is prepared such that the (A) component and (B) component and other components used as needed are preferably a liquid composition dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylethyl Acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, Ethylene glycol methyl ether, ethylene glycol ethyl 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, ethyl carbonate, propyl carbonate, etc. These organic solvents can 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 mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., preferably 1 The range of mass% to 10 mass%. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate by the method described below, and is preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, making it difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large, making it difficult to obtain a good liquid crystal alignment film. In addition, there is an increase in viscosity of the liquid crystal alignment agent and a decrease in coatability tendency.

[Liquid crystal alignment film and liquid crystal element] The liquid crystal alignment film of the present invention can be formed using the liquid crystal alignment agent prepared in the above-described manner. In addition, the liquid crystal element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, it can be applied to a twisted nematic (TN) type, a super twisted nematic (STN) type, and a vertical alignment (VA) Type (including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), coplanar Switching (In-Plane Switching, IPS) type, fringe field switching (FFS) type, optically compensated bending (Optically Compensated Bend, OCB) type and other operating modes.

The method of manufacturing the liquid crystal element using the liquid crystal alignment agent is not particularly limited, and from the viewpoint of being suitable for obtaining the effects of the present invention, it is preferably manufactured by a method including the following steps: (1) The step of applying a liquid crystal alignment agent to the conductive film of the substrate, and then heating it to form a coating film; (2) A pair of substrates forming a coating film are opposed to each other with the liquid crystal layer interposed therebetween The step of arranging the liquid crystal cell in the opposite arrangement; and (3) The step of irradiating the liquid crystal cell with a voltage applied between the conductive films of the pair of substrates.

[Step (1): Formation of coating film] For the substrate coated with the liquid crystal alignment agent, for example, glass such as float glass and soda glass; including polyethylene terephthalate and polybutylene terephthalate can be used. Transparent substrates such as plastics such as ester, polyether ballast, and polycarbonate. Substrate having a conductive film is preferably a transparent conductive film, for example, may be used comprise SnO Naise (NESA) ₂ (registered trademark) film, indium-tin-containing In ₂ O ₃ -SnO ₂ oxide (Indium Tin Oxide, ITO ) Membrane etc. In order to apply the liquid crystal alignment agent on the conductive film of the substrate, a suitable coating method such as a roll coater method, a spinner method, an offset printing method, and an inkjet printing method can be used. After the liquid crystal alignment agent is applied, for the purpose of preventing sagging of the applied alignment agent, it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30°C to 200°C. The pre-baking time is preferably 0.25 minutes to 10 minutes. Then, for the purpose of completely removing the solvent, and additionally for the purpose of thermally imidizing the amide acid structure present in the polymer as needed, a sintering (post-baking) step is performed. The burning temperature (post-baking temperature) at this time is preferably 80°C to 300°C. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm. The coating film formed in the above-mentioned manner may be directly provided to the manufacture of the liquid crystal cell, or may be provided to the manufacture of the liquid crystal cell after rubbing treatment. This rubbing treatment can be performed by wiping the coating film in a certain direction by using a roller wound with a cloth containing fibers such as nylon, rayon, and cotton.

[Step (2): Construction of liquid crystal cell] Next, the pair of substrates on which the coating film is formed are opposed to each other with the coating film interposed therebetween to form a liquid crystal cell. The thickness of the liquid crystal layer is preferably 1 μm to 5 μm. The liquid crystal contained in the liquid crystal layer is preferably a nematic liquid crystal having negative dielectric anisotropy. For example, dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, Schiff base-based liquid crystals, and oxides can be used. Azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, etc. In terms of being able to shorten the process time of the liquid crystal filling step, the method of manufacturing the liquid crystal cell preferably adopts the following method (ODF method): a predetermined portion on one of the two substrates on which the liquid crystal alignment film is formed, For example, after applying a UV-curable sealant, and then dropping liquid crystal on the surface of the liquid crystal alignment film, the other substrate is bonded in a manner that the liquid crystal alignment film faces, 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. It is desirable that the manufactured liquid crystal cell is further heated to a temperature at which the liquid crystal used acquires an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment (annealing) when the liquid crystal is filled. The heating temperature at this time is preferably 50°C to 150°C, and the heating time is preferably 10 minutes to 2 hours. For the sealant, for example, an epoxy resin containing a hardener and alumina balls as spacers can be used.

[Step (3): Light Irradiation Process] Next, the liquid crystal cell manufactured as described above was irradiated with light while applying a voltage between the conductive films included in the pair of substrates. The applied voltage may be, for example, 5 V to 50 V DC or AC. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, and preferably ultraviolet rays including light having a wavelength of 300 nm to 400 nm. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The irradiation amount of light is preferably 1,000 J/m ² to 100,000 J/m ² , and more preferably 1,000 J/m ² to 50,000 J/m ² .

Next, a polarizing plate is bonded to the outer surface of the liquid crystal cell after the above-mentioned treatment as necessary, whereby a liquid crystal element can be obtained. Examples of the polarizing plate used herein include a polarizing plate in which a polarizing film called "H film" is sandwiched with a cellulose acetate protective film, a polarizing plate including the H film itself, etc. The "H film" It is a film made by absorbing iodine while extending and aligning polyvinyl alcohol.

The liquid crystal element of the present invention can be effectively used in various applications, such as: watches, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistant, PDA) ), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices, or phase difference films, dimming films, etc. [Example]

Hereinafter, the present invention will be further specifically described by examples, but the present invention is not limited to these examples. In the following examples, the weight average molecular weight of the polymer, the imidate ratio of the polyimide, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following method. [Weight average molecular weight of polymer (Mw)] A polystyrene conversion value measured by gel permeation chromatography under the following conditions. Column: manufactured by Tosoh (share), TSKgelGRCXLII Solvent: N,N-dimethylformamide solution containing tetrahydrofuran, or lithium bromide and phosphoric acid Temperature: 40°C Pressure: 68 kgf/cm ² [Polyamide] Amine imidization rate of amine]: Put the solution containing polyimide into pure water, and after fully drying the resulting precipitate under reduced pressure at room temperature, dissolve it in deuterated dimethyl sulfoxide, Based on silane as a reference substance, ¹ H-nuclear magnetic resonance (NMR) was measured at room temperature. Based on the obtained ¹ H-NMR spectrum, the imidate ratio [%] was determined using the following mathematical formula (1). Acetylimidization rate [%] = (1-A ¹ /A ² ×α)×100…(1) (In the mathematical formula (1), A ¹ is derived from the NH group near the chemical shift of 10 ppm The peak area of protons, A ² is the peak area derived from other protons, α is the ratio of the number of other protons relative to one proton of the NH group in the polymer precursor (polyamide) Solution viscosity (mPa·s)]: For a solution prepared with a predetermined solvent and having a polymer concentration of 10% by mass, it is measured at 25°C using an E-type viscometer. [Epoxy equivalent]: Measured in accordance with "hydrochloric acid-methyl ethyl ketone method" of JIS C2105. In addition, in the following, the compound represented by the formula X may be abbreviated as "compound X".

<Synthesis of (A) component> [Synthesis Example 1-1] 110 g (0.50 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride was used as the diamine compound 43 g (0.40 mol) of p-phenylenediamine and 52 g (0.10 mol) of 3-(3,5-diaminobenzyloxy)cholesterane, dissolved in 830 g of N-methyl In N-methyl-2-pyrrolidone (NMP), the reaction was carried out at 60°C for 6 hours. A small amount of the obtained polyamic acid solution was added, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The result was 60 mPa·s. Then, 1900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure was performed at 110° C. for 4 hours. After the amide imidization reaction, the solvent in the system was replaced with a new NMP (by this operation, the pyridine and acetic anhydride used in the amide imidization reaction were removed to the outside of the system) to obtain about 15% by mass A solution of polyimide (polymer (PIm-1)) with an imidization rate of about 50%. A small amount of the obtained polyimide solution was added and NMP was added to prepare a solution having a polyimide concentration of 10% by mass. The measured solution viscosity was 47 mPa·s.

[Synthesis Example 1-2] 110 g (0.50 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 22 g (0.20 mole) of diamine compound P-phenylenediamine, 30 g (0.20 mol) of 3,5-diaminobenzoic acid and 52 g (0.10 mol) of 3-(3,5-diaminobenzyloxy)cholesterol Alkane, dissolved in 860 g of NMP, was reacted at 60°C for 6 hours. A small amount of the obtained polyamic acid solution was added, NMP was added, and the viscosity was measured with a solution with a solid content concentration of 10%. The result was 58 mPa·s. Then, 1800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration and ring closure were performed at 110° C. for 4 hours. After the amide imidization reaction, the solvent in the system was replaced with a new NMP to obtain a polyimide (polymer (PIm-2)) containing about 15% by mass of the imidate ratio of about 50%. The solution. A small amount of the obtained polyimide solution was added and NMP was added to prepare a solution having a polyimide concentration of 10% by mass. The measured solution viscosity was 69 mPa·s.

[Synthesis Example 2-1] 110 g (0.50 mole) of tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentylacetic acid dianhydride were used as 52 g (0.10 mole) of the diamine compound Of 3-(3,5-diaminobenzyloxy)cholesterane, 11 g (0.10 mol) of p-phenylenediamine and 45 g (0.30 mol) of 2,5-diaminobenzene Formic acid, dissolved in 870 g of NMP, was reacted at 60°C for 6 hours. NMP was added for dilution, and adjusted so that the polyamic acid concentration became 10% by mass, thereby obtaining a solution containing polyamic acid (polymer (PAm-1)). The solution viscosity of the polyamide solution is 120 mPa·s.

[Synthesis Example 2-2] 200 g (1.0 mole) of tetracarboxylic dianhydride was used as 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 52 g (0.1 mole of diamine compound) Ear) 3-(3,5-diaminobenzyloxy)cholesterane and 191 g (0.9 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl , Dissolved in 3,990 g of NMP, and reacted at 40° C. for 3 hours, thereby obtaining a solution containing 10% by mass of polyamic acid (polymer (PAm-2)). The solution viscosity of the polyamide solution is 90 mPa·s.

[Synthesis Example 3-1] 12.69 g (80 mol parts relative to the total amount of 100 mol parts of the diamine used in the synthesis) as a diamine compound was added 4,4′-diaminodiphenyl Methane and 8.37 g (20 mol parts relative to 100 mol parts of the total amount of diamine used in the synthesis) 3-(3,5-diaminobenzyloxy)cholesterane, as a base 15 ml of pyridine and 505 ml of N-methyl-2-pyrrolidone (NMP) as a solvent were dissolved. While the solution was cooled and stirred in a water bath, 23.05 g (97 mol parts relative to 100 mol parts of the total amount of diamine used in the synthesis) was added Cyclobutane-2,4-carboxylic acid ester was further added with NMP so that the solid content concentration became 5% by mass, and stirred for 4 hours while cooling in a water bath. The solution was poured into 250 g of water to precipitate the polymer, and the polymer was filtered by suction filtration, washed again with 250 g of water, and then washed with 63 g of methanol three times at 40°C It was dried under reduced pressure, whereby 36 g of polyamide powder was obtained. Using NMP, this polyamide (polymer (PAE-1)) was prepared so as to become 10% by mass.

[Synthesis Example 4-1] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyl as a hydrolyzable silane compound was added Trimethoxysilane, 500 g of methyl isobutyl ketone as a solvent, and 10.0 g of triethylamine as a catalyst were mixed at room temperature. To this, 100 g of deionized water was added dropwise from a dropping funnel over 30 minutes, and the reaction was carried out at 80° C. for 6 hours while mixing under reflux. After the reaction was completed, the organic layer was taken out, and the organic layer was washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to use a viscous transparent liquid The polyorganosiloxane with epoxy groups is obtained. ¹ H-NMR analysis of the epoxy-containing polyorganosiloxane was carried out, and as a result of theoretical intensity, an epoxy-based peak was obtained near the chemical shift (δ) = 3.2 ppm, confirming that no epoxy was generated in the reaction Side reactions. The epoxy equivalent of this epoxy group-containing polyorganosiloxane was measured and found to be 186 g/equivalent. Then, in a 200 mL three-necked flask, 10.0 g of the obtained epoxy-containing polyorganosiloxane, 30.28 g of methyl isobutyl ketone as a solvent, and 3.87 g of carboxylic acid (relative 4-(4-pentylcyclohexyl)benzoic acid based on the epoxy group of epoxy-containing polyorganosiloxane equivalent to 25 mol%, and 0.10 g of UCAT18X (trade name, Sanya) as a catalyst (Produced by San-Apro Co., Ltd.), and the reaction was carried out at 100°C for 48 hours with stirring. After the reaction was completed, ethyl acetate was added to the reaction mixture to obtain a solution. The solution was washed three times with water and the solvent was distilled off, thereby obtaining 9.5 g of a polyorganosiloxane (polymer (PSi -1)). The weight average molecular weight Mw of the obtained polymer (PSi-1) was 5,500.

[Synthesis Example 5-1] In a reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube, 3,4-epoxycyclohexyl methyl methacrylate (ECMMA, which is a polymerizable unsaturated monomer, is added to the polymerization vessel). The total amount of monomers used in 100 mole parts is 60 mole parts), and 2-hydroxyethyl methacrylate (HEMA) is 15 moles relative to the total amount of 100 mole parts of monomers used in polymerization Parts), N-cyclohexyl maleic diimide (CMI, 10 moles relative to 100 moles of the total amount of monomers used in the polymerization), and styrene (ST, relative to polymerization The total amount of monomers used in 100 mole parts is 15 mole parts), and diethylene glycol ethyl methyl ether is added to dissolve so that the total amount of polymerizable unsaturated monomers becomes 50% by mass. To this, 2,2'-azobis(2,4-dimethylvaleronitrile), which is 3 mol% relative to the total number of moles of the polymerizable unsaturated monomer as a polymerization initiator, and as The α-methylstyrene dimer of the chain transfer agent, which is 0.5 times the mass of the polymerization initiator. Then, bubbling was carried out for 10 minutes under a nitrogen flow to perform nitrogen replacement in the system, and then a polymerization reaction was carried out at 70°C for 5 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. After washing the recovered precipitate with methanol, it was dried under reduced pressure at 40°C for 15 hours, thereby obtaining an methacrylate copolymer having an epoxy group. Then, in a 200 mL three-necked flask, 10.0 g of the obtained epoxy-containing methacrylate copolymer, 30.28 g of methyl isobutyl ketone as a solvent, and 4.01 g of carboxylic acid (relative Epoxy group-containing methacrylate copolymer used in the polymerization, which corresponds to 25 mol%) 4-(4-pentylcyclohexyl)benzoic acid, and 0.10 g of UCAT18X (trade name, Sanya Apro (manufactured by San-Apro Co., Ltd.), and the reaction was carried out at 90°C for 12 hours with stirring. After the reaction was completed, ethyl acetate was added to the reaction mixture to obtain a solution, and the solution was washed three times with water. The organic layer after washing with water was poured into a large amount of excess methanol to precipitate a polymer, and the recovered precipitate was dried at 40°C for 12 hours, thereby obtaining 10.5 g of a polymer (PAc) having a liquid crystal alignment group Methacrylate copolymer (polymer (PAc-1)). The weight average molecular weight Mw of the obtained polymer (PAc-1) was 16,800.

<Synthesis of (B) component> [Synthesis Example 6-1] The compound (DM-1) was synthesized by the following scheme 1. [化21]

In a 2 L three-necked flask equipped with a dropping funnel and a thermometer, add 42.8 g (0.2 mol) of 4-(4-hydroxyphenyl)benzoic acid, 16 g (0.4 mol) of sodium hydroxide, and 1 L of water, After dissolving evenly, cool to below 5℃. Next, 23.4 mL (0.24 mol) of methacryloyl chloride and 300 mL of dichloromethane were added to the dropping funnel, and the solution was added dropwise at 5°C for 2 hours, returned to room temperature, and further reacted for 3 hours. After the reaction was completed, the white precipitate recovered by filtration was dissolved in 1 L of ethyl acetate and 2 L of tetrahydrofuran, washed once with 1 L of 1 M hydrochloric acid aqueous solution, and washed three times with 500 mL of water. Next, after the organic layer was dried with magnesium sulfate, it was concentrated to about 500 mL, and the obtained white crystal was recovered and dried to obtain 56.4 g of a compound (DM-1-1) as a white crystal. Then, in a 500 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 8.03 g (28.4 mmol) of the compound (DM-1-1), 9.89 g (71.1 mmol) of 2,6-pyridinedimethanol, 150 mL of tetrahydrofuran and 30 mL of N,N-dimethylformamide were suspended and cooled in an ice bath. Next, add 8.17 g (42.6 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.70 g (5.73 mmol) of N,N-dimethyl The aminoaminopyridine was stirred under ice bath cooling for 2 hours, then returned to room temperature, and reacted for 16 hours. After the reaction was completed, 1 L of ethyl acetate was added, washed with water three times, and then dried with magnesium sulfate. The precipitate produced by concentration was purified with a silica column (developing solvent: methylene chloride/hexane/ethyl acetate=1:1:1), concentrated, and dried in vacuo to obtain 7.82 g of a compound (DM -1-2) White precipitate. Then, in a 200 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 5.46 g (13.5 mmol) of the compound (DM-1-2), 1.75 g (20.3 mmol) of methacrylic acid, and 50 mL of dichloromethane were added Methane is dissolved and cooled in an ice bath. Next, add 3.89 g (20.3 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 330 mg (2.7 mmol) of N,N-dimethyl The aminoaminopyridine was stirred under ice bath cooling for 2 hours, then returned to room temperature, and reacted for 16 hours. After the reaction was completed, it was purified using a silica column (developing solvent: dichloromethane/ethyl acetate = 10:1), and concentrated. After adding 700 mL of ethyl acetate, the solution was washed with water three times. Dry with magnesium sulfate. Next, the white precipitate produced by concentration was filtered and dried, thereby obtaining 4.21 g of white crystals of the compound (DM-1).

[Synthesis Example 6-2 to Synthesis Example 6-5] The compound was synthesized in the same manner as in Synthesis Example 6-1 except that the compound shown below was used instead of 2,6-pyridine dimethanol. Compounds represented by formula (DM-2) to formula (DM-5), respectively. Synthesis Example 6-2 (synthesis of compound (DM-2)): 1,3-(hydroxymethyl)urea Synthesis Example 6-3 (synthesis of compound (DM-3)): 1,3-(hydroxymethyl) ) Thiourea Synthesis Example 6-4 (Synthesis of Compound (DM-4)): N-phenyldiethanolamine Synthesis Example 6-5 (Synthesis of Compound (DM-5)): N-Methyldiethanolamine

[Synthesis Example 6-6: Synthesis of compound (DM-6)] The compound (DM-6) was synthesized by the following scheme 2. [化22]

In a 300 mL three-necked flask equipped with a cooling tube, add 10 g (35.4 mmol) of the compound (DM-1-1) and 6.95 g (35.4 mmol) of 3,4-epoxycyclohexyl methyl methacrylate , 85 mL of methyl isobutyl ketone as a solvent, and 0.24 g of UCAT18X (trade name, manufactured by San-Apro) as a catalyst, under stirring at 70°C for 12 hours reaction. After the reaction was completed, ethyl acetate was added to the reaction mixture to obtain a solution, and the solution was washed three times with water and then dried with magnesium sulfate. Next, the white precipitate produced by concentration was filtered and dried to obtain 13.7 g of white crystals of the compound (DM-6-1) (mixture of positional isomers). Then, in a 30 mL eggplant-shaped flask equipped with a reflux tube, 2.78 g (20.3 mmol) of 3-pyridylacetic acid, 2.2 mL (30.5 mmol) of sulfenyl chloride and 0.1 g of N,N-dimethyl Carboxamide, reflux for 1 hour. After the reaction was completed, the sulfenyl chloride was distilled off by concentration under reduced pressure, and 20 mL of dichloromethane was added (this solution is referred to as "A1 liquid"). On the other hand, in a 200 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 6.46 g (13.5 mmol) of the compound (DM-6-1) and 50 mL of methylene chloride as a solvent were added and dissolved, Perform ice bath cooling. Next, the A1 liquid just prepared was added dropwise for 3 hours under ice-cooling, and the reaction was further performed at room temperature for 1 hour. After the reaction was completed, 500 mL of ethyl acetate was added, washed with water three times, and dried with magnesium sulfate. Next, the white precipitate produced by concentration was filtered and dried, thereby obtaining 7.34 g of white crystals of the compound (DM-6) (mixture of positional isomers).

[Synthesis Example 6-7 to Synthesis Example 6-10] The above formula (Synthesis Formula 6-6) was synthesized in the same manner as in Synthesis Example 6-6 except that the compound shown below was used instead of 3-pyridylacetic acid. DM-7) to compounds represented by formula (DM-10). Synthesis Example 6-7 (Synthesis of Compound (DM-7)): 1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid Synthesis Example 6-8 (Synthesis of Compound (DM-8)): ( 2-methyl-1H-imidazol-1-yl)acetic acid synthesis example 6-9 (synthesis of compound (DM-9)): 3-guanidinopropionic acid synthesis example 6-10 (synthesis of compound (DM-10) ): 4-(4,5-dihydro-1H-imidazol-2-ylamino)butanoic acid

[Synthesis Example 6-11] The compound (DM-52) was synthesized in the following scheme 3. [化23]

In a 200 mL eggplant-shaped flask equipped with a cooling tube, add 14.1 g (50.0 mmol) of the compound (DM-1-1) and 71.4 g (600 mmol) of thionyl chloride at 80°C with stirring 1 hour reaction. After the reaction, excess sulfenyl chloride was distilled off by concentration under reduced pressure to dry it. The obtained solid was washed with hexane and dried, thereby obtaining 14.9 g of a compound (DM-1-1-Cl) as white crystals. Then, in a 500 mL three-necked flask, 2.22 g (30.0 mmol) of 1-hydroxy-2,3-epoxypropane, 4.75 g (60.0 mmol) of pyridine, and 300 mL of dichloromethane were added, followed by an ice bath cool down. A solution obtained by dissolving 9.20 g (30.6 mmol) of the compound (DM-1-1-Cl) in 50 mL of dichloromethane was added dropwise thereto, and the reaction was carried out at room temperature with stirring for 5 hours. After the reaction, the reaction solution was washed three times with water. Next, the concentrated residue was purified by silica gel chromatography to obtain 7.95 g of compound (DM-52) as white crystals.

[Synthesis Example 6-12] The compound (DM-56) was synthesized in the following scheme 4. [化24]

In a 2000 mL three-necked flask, add 10.5 g (100 mmol) of the compound 2,2'-dihydroxydiethylamine, 9.25 g (100 mmol) of epichlorohydrin, and 12.1 g (120 mmol) of triethyl Amine and 1000 mL of tetrahydrofuran were reacted under stirring at 40°C for 10 hours. The solid produced by concentrating the reaction liquid was removed by filtration, and the filtrate was concentrated to obtain 13.6 g of a compound (EDHA) as a yellow oil. Next, 5.64 g (35.0 mmol) of the compound (EDHA), 8.50 g (84.0 mmol) of triethylamine, and 350 mL of dichloromethane were added to a 1000 mL three-necked flask, and ice bath cooling was performed. A solution prepared by dissolving 23.2 g (38.5 mmol) of the compound (DM-1-1-Cl) in 100 mL of methylene chloride was added dropwise, and the reaction was carried out at room temperature with stirring for 5 hours. After the reaction, the reaction solution was washed three times with water. Next, the concentrated residue was purified by silica gel chromatography to obtain 22.0 g of compound (DM-56) as white crystals.

[Synthesis Example 6-13 and Synthesis Example 6-14] In addition to the use of the compound shown below instead of 1-hydroxy-2,3-epoxypropane, Compound (DM-1-1-Cl) was used to synthesize compound (DM-52). In the same way, compound (DM-66) (where n=3) and compound (DM-72) were synthesized. Synthesis Example 6-13 (Synthesis of Compound (DM-66) (n=3)): Synthesis Example 6-14 of 3-(Dimethylamino)-1-propanol (Synthesis of Compound (DM-72)) : Methyl 4-hydroxycyclohexyl carbamate

[Synthesis Example 6-15] The compound (DM-76) was synthesized in the following scheme 5. [化25]

In a 1000 mL three-necked flask, add 5.96 g (50.0 mmol) of 3-aminopentane-1,5-diol, 6.07 g (60.0 mmol) of triethylamine, and 500 mL of tetrahydrofuran, and perform an ice bath . A solution obtained by dissolving 5.20 g (55.0 mmol) of methyl carbonochloridate in 100 mL of dichloromethane was added dropwise, and the reaction was carried out under stirring at room temperature for 5 hours. After the reaction, the reaction solution was washed three times with water. The solid produced by concentrating the reaction liquid was removed by filtration, and the filtrate was concentrated, thereby obtaining 17.2 g of a compound (BIDHA) as a yellow oil. The subsequent reaction uses the same method as the method for synthesizing the compound (DM-55) from the compound (EDHA) in Synthesis Example 6-12 except that the compound (BIDHA) is used instead of the compound (EDHA). (DM-76).

[Synthesis Example 6-15] The above formula was synthesized in the same manner as in Synthesis Example 6-1 except that in the above Scheme 1, acrylic acid was reacted with the compound (DM-1-2) instead of methacrylic acid. The compound represented by (DM-78).

[Example 1] (1) Preparation of liquid crystal alignment agent The polymer (PIm-1) obtained in Synthesis Example 1-1 as 80 parts by mass of (A) component, and 20 parts by mass of (B) component To the compound (DM-1) obtained in Synthesis Example 6-1, NMP and butyl cellosolve (BC) were added to produce a solid content concentration of 6.5% by mass and a solvent mixing ratio of NMP: BC=50:50 ( Mass ratio) solution. After the solution was sufficiently stirred, it was filtered through a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Manufacture of liquid crystal cells Using a liquid crystal alignment film printer (manufactured by Japan Photographic Printing Co., Ltd.), the liquid crystal alignment agent prepared in (1) above was applied to an ITO electrode structure having fine slits respectively On the transparent electrode surface of the glass substrate with a transparent electrode and the glass substrate with a transparent electrode having a patterned ITO electrode structure. Then, after heating (pre-baking) for 1 minute on an 80°C hotplate to remove the solvent, heating (post-baking) for 10 minutes on a 200°C hotplate to form a coating film with an average film thickness of 800 Å. Each substrate after the formation of the coating film was subjected to ultrasonic washing in ultrapure water for 1 minute, followed by drying in a clean oven at 100°C for 10 minutes. By this, a pair (two pieces) of substrates having a liquid crystal alignment film is obtained. Next, the outer edge of the substrate is formed on the coating film with a thin slit ITO electrode structure, and a photocurable epoxy acrylic resin-based adhesive added with an alumina spacer with a diameter of 3.5 μm is applied, and the required amount is added dropwise LCD (MLC-6608, manufactured by Merck). At this time, liquid crystal is dropped on a plurality of places on the coating film forming substrate. In addition, with respect to the volume obtained by multiplying the area to which the adhesive is applied and the diameter of the spacer, the total amount of liquid crystals dropped is set to 0.98 times to 1.0 times, and the amount of drops per point is 0.2 g to Adjust between 1.0 g. Then, the substrate to which the liquid crystal was dropped was set in a vacuum bonding apparatus, and a coating film having a patterned ITO electrode structure was provided on the opposite side of the substrate to form the substrate, and then bonding was performed under vacuum. In addition, the operation so far is carried out at room temperature. After bonding, the adhesive part was hardened using UV light at 365 nm, and then annealed in an oven at 120° C. for 1 hour to obtain a liquid crystal cell. Then, for the obtained liquid crystal cell, an AC 10 V with a frequency of 60 Hz was applied between the electrodes, and in a state where the liquid crystal was driven, an ultraviolet irradiation device using a metal halide lamp as the light source was used at a rate of 50,000 J/m ² . Irradiate the amount of ultraviolet light. In addition, this irradiation amount is the value measured using the photometer which measured based on the wavelength 365 nm reference. The following evaluation was performed using the liquid crystal cell after light irradiation.

(3) Evaluation of response speed For the liquid crystal cell manufactured in (2) above, first, a visible light lamp was irradiated without applying a voltage, and the brightness of light transmitted through the liquid crystal cell was measured using a photo multimeter, and this value was taken as The relative transmittance is 0%. Next, the transmittance when 5 V AC was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and this value was regarded as the relative transmittance of 100%. When 5 V AC was applied to the liquid crystal cell, the time until the relative transmittance changed from 10% to 90% was measured, and this time was defined as the response speed and evaluated. The evaluation is performed as follows: the case where the response speed is less than 8 msec is judged as high-speed responsiveness "excellent", the case where 8 msec or more and less than 15 msec is judged as high-speed responsiveness "good", and the case where 15 msec or more is less than 20 msec The case is judged as high-speed responsiveness "OK", and the case of 20 msec or more is judged as "high-speed responsiveness". As a result, in this example, the response speed of the liquid crystal cell was 5 msec, which was "excellent".

(4) Evaluation of ODF unevenness The liquid crystal cell manufactured in the above (2) was applied with a 60 V AC voltage of 2.5 V, and the unevenness (ODF unevenness) generated in the entire liquid crystal cell was observed. A case where no unevenness occurred was evaluated as "excellent", and a case where a slight unevenness was seen in at least any one of the liquid crystal dropping position and the middle of the liquid crystal dropping position was evaluated as "good", and the liquid crystal drop A case where a strong unevenness was observed in at least any one of the addition position and the liquid crystal dropping position was evaluated as "bad", and as a result, the ODF unevenness of the liquid crystal cell was evaluated as "good".

[Example 2 to Example 35 and Comparative Example 1 to Comparative Example 5] Except that the types and amounts of components (A), (B) and other components are set as described in Table 1 below, the In the same manner as in Example 1, a liquid crystal alignment agent was prepared, a liquid crystal cell was manufactured using the liquid crystal alignment agent, and various evaluations were performed. In addition, in Example 3, Example 4, Example 20 to Example 23, and Example 25, two types were used as the (A) component, and in Example 33 to Example 35, other components were further formulated. The evaluation results are shown in Table 1 below.

[Table 1]

In Table 1, the numerical values in the columns of (A) component, (B) component, and other components represent a total of 100 parts by mass relative to the solid components (all components other than the solvent in the liquid crystal alignment agent) used in the preparation of the liquid crystal alignment agent In terms of the compounding ratio of each compound (parts by mass). The abbreviations in Table 1 have the following meanings. DM-55: the compound represented by the formula (DM-55) dm-1: ethylene oxide (EO) modified bisphenol A dimethacrylate (trade name FA-321M, Hitachi Chemical Industry) (Production) dm-2: 4,4'-isopropylenediphenol dimethacrylate dm-3: compound represented by the following formula (dm-3)

As shown in Table 1, in Examples 1 to 35 containing the (B) component, the ODF unevenness was small, and the response speed of the liquid crystal cell was also fast. In addition, in Examples including a polymer having a partial structure derived from a carboxyl group-containing diamine, it is seen that the response speed becomes faster and the ODF unevenness tends to be less. On the other hand, in Comparative Examples 1 to 4 not containing the (B) component, the ODF was not all evaluated as "poor", and in Comparative Example 5, the response speed was evaluated as "poor". Based on the above results, it was confirmed that the liquid crystal alignment film used in Examples does not deteriorate the response speed, and can suppress ODF unevenness.

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Claims (6)

A liquid crystal alignment agent, comprising the following components (A) and (B): component (A): selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane and having polymerization At least one polymer in the group consisting of polymers of monomers having a unsaturated bond; (B) component: a photopolymerizable compound represented by the following formula (D-1):

In formula (D-1), Y ¹ includes a partial structure selected from the following formula (1), a partial structure represented by the following formula (2), and a partial structure represented by the following formula (3), A divalent group of at least one of the group consisting of tertiary amine structure, nitrogen-containing heterocyclic structure and -NR ³¹ X ¹⁰ , wherein R ³¹ is a monovalent hydrocarbon group, X ¹⁰ is a protecting group; X ⁶ is a hydrogen atom, Fluorine atom, C 1-6 alkyl group, C 1-6 fluoroalkyl group or C 6-12 monovalent aromatic ring group, R ³ is oxygen atom, sulfur atom or -NH-, Ar ¹ and Ar ^{2 is} independently 1,4-phenylene, 1,4-cyclohexyl, naphthyl, tetrahydronaphthalenediyl, or decahydronaphthalenediyl, and may have a substituent in the ring portion; R ⁴ Is a single bond, an ester bond, an amide bond, an ether bond, or -CO-NR ³⁴ -, where R ³⁴ is a protecting group, and R ⁵ is an ester bond, an amide bond, an ether bond, or -CO-NR ³⁵ -, Where R ³⁵ is a protecting group; R ⁷ is a single bond, ester bond, amide bond, ether bond, or -CO-NR ³⁶ -, wherein R ³⁶ is a protecting group; R ⁸ is a single bond, alkanediyl, benzene stretch Group, cyclohexyl group, or divalent group represented by the following formula (6); n1 is an integer of 0~2; when n1=2, R ⁴ and Ar ² independently have the above definition; multiple X ⁶ and multiple R ³ independently have the definition;

In formula (1), X ⁴ is an oxygen atom or a sulfur atom, R ² is an oxygen atom, a sulfur atom, an alkanediyl group, an aromatic ring group, a cyclohexyl group, or -NR ³² -, wherein R ³² is a hydrogen atom or a protection Group, R ³⁰ is a hydrogen atom or a protecting group; wherein, when R ² is an aromatic ring group or a cyclohexyl group, R ³⁰ is a protecting group; in formula (2), X ⁵ is a divalent hydrocarbon group or -NR ³³ -, wherein R ³³ is a hydrogen atom or a protecting group; "*" represents a bonding bond;

In formula (6), Ar ³ and Ar ⁴ are independently 1,4-phenylene or 1,4-cyclohexyl, X ⁸ is a single bond or -COO-; n2 is 1 or 2; when n2= At 2 o'clock, Ar ⁴ and X ⁸ each independently have the above definition; "*" indicates a bonding bond. The liquid crystal alignment agent according to item 1 of the patent application scope, wherein the component (A) is at least one selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester, and It includes a polymer having a partial structure derived from a diamine having a carboxyl group. A method of manufacturing a liquid crystal element, which is a method of manufacturing a liquid crystal element, comprising: applying liquid crystals as described in item 1 or item 2 of the patent application range to the conductive films of a pair of substrates having a conductive film, respectively A step of forming a coating film by an alignment agent; a step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed to face each other with the coating film facing each other through a liquid crystal layer; and The step of irradiating the liquid crystal cell with a voltage applied between the films. A liquid crystal alignment film formed using the liquid crystal alignment agent as described in the first or second patent application. A liquid crystal element including the liquid crystal alignment film as described in item 4 of the patent application. A compound represented by the following formula (D-1):

In formula (D-1), Y ¹ includes a partial structure selected from the following formula (1), a partial structure represented by the following formula (2), and a partial structure represented by the following formula (3), At least one divalent group in the group consisting of tertiary amine structure, nitrogen-containing heterocyclic structure and -NR ³¹ X ¹⁰ , wherein R ³¹ is a monovalent hydrocarbon group, X ¹⁰ is a protecting group; X ⁶ is a hydrogen atom, Fluorine atom, C 1-6 alkyl group, C 1-6 fluoroalkyl group or C 6-12 monovalent aromatic ring group, R ³ is oxygen atom, sulfur atom or -NH-, Ar ¹ and Ar ^{2 is} independently 1,4-phenylene, 1,4-cyclohexyl, naphthyl, tetrahydronaphthalenediyl, or decahydronaphthalenediyl, and may have a substituent in the ring portion; R ⁴ Is a single bond, an ester bond, an amide bond, an ether bond, or -CO-NR ³⁴ -, where R ³⁴ is a protecting group, and R ⁵ is an ester bond, an amide bond, an ether bond, or -CO-NR ³⁵ -, Where R ³⁵ is a protecting group; R ⁷ is a single bond, ester bond, amide bond, ether bond, or -CO-NR ³⁶ -, wherein R ³⁶ is a protecting group; R ⁸ is a single bond, alkanediyl, benzene stretch Group, cyclohexyl group, or divalent group represented by the following formula (6); n1 is an integer of 0~2; when n1=2, R ⁴ and Ar ² independently have the above definition; multiple X ⁶ and multiple R ³ independently have the definition;

In formula (1), X ⁴ is an oxygen atom or a sulfur atom, R ² is an oxygen atom, a sulfur atom, an alkanediyl group, an aromatic ring group, a cyclohexyl group, or -NR ³² -, wherein R ³² is a hydrogen atom or a protection Group, R ³⁰ is a hydrogen atom or a protecting group; wherein, when R ² is an aromatic ring group or a cyclohexyl group, R ³⁰ is a protecting group; in formula (2), X ⁵ is a divalent hydrocarbon group or -NR ³³ -, wherein R ³³ is a hydrogen atom or a protecting group; "*" represents a bonding bond;

In formula (6), Ar ³ and Ar ⁴ are independently 1,4-phenylene or 1,4-cyclohexyl, X ⁸ is a single bond or -COO-; n2 is 1 or 2; when n2= At 2 o'clock, Ar ⁴ and X ⁸ each independently have the above definition; "*" indicates a bonding bond.