WO2020148953A1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent which exhibits good coatability to a substrate but is not likely to deteriorate an inkjet head, and which enables the achievement of a liquid crystal element that has excellent afterimage characteristics. According to the present invention, a liquid crystal aligning agent is configured to contain a polymer component and a component (A) that is represented by formula (1).　(1): (R2)x-Ar1-R1 (In formula (1), Ar1 represents an aromatic ring group having a valence of (x + 1); R2 represents an alkyl group having 1-3 carbon atoms, a hydroxyalkyl group having 1-3 carbon atoms or an alkoxy group having 1-3 carbon atoms; x represents 0 or 1; and R1 represents a hydroxyalkyl group having 1-3 carbon atoms or an alkoxy group having 1-3 carbon atoms.)

Description

Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal element Cross-reference of related applications

This application is based on Japanese Patent Application No. 2019-6186 filed on January 17, 2019, the content of which is incorporated herein by reference.

The present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal element.

The liquid crystal element has a liquid crystal alignment film having a function of aligning liquid crystal molecules in a liquid crystal layer in a certain direction. The liquid crystal aligning film is generally formed on the substrate by applying a liquid crystal aligning agent in which a polymer component is dissolved in an organic solvent onto the surface of the substrate, and preferably by heating. As the solvent component of the liquid crystal aligning agent, N-methyl-2-pyrrolidone, γ-butyrolactone and the like are generally used as a solvent (good solvent) having high solubility of the polymer component. Further, it has been performed to improve wettability and spreadability on a substrate by mixing a solvent (poor solvent) having low solubility of a polymer component such as butyl cellosolve with these good solvents (for example, patent (See Reference 1 and Patent Reference 2).

In recent years, by using a large line to increase the size of the substrate, the size of the liquid crystal display device can be increased, or by taking a plurality of panels from one substrate, the time and cost of the manufacturing process can be reduced. Are being reduced. On the other hand, if the size of the substrate is increased, the application area of the liquid crystal aligning agent becomes large in area, so that it becomes difficult to secure the uniformity of the film quality over the entire application area. In order to solve such a problem of coating properties, in recent years, a coating method by an inkjet printing method has been introduced in a manufacturing process of a large liquid crystal panel.

JP, 2017-198975, A JP, 2016-206645, A

N-methyl-2-pyrrolidone and γ-butyrolactone are excellent in solubility of the polymer component of the liquid crystal aligning agent, and therefore, when the liquid crystal aligning agent is applied on the substrate by the inkjet printing method in the production of a large liquid crystal panel. Therefore, it is possible to reduce the unevenness of application of the liquid crystal aligning agent. On the other hand, N-methyl-2-pyrrolidone and γ-butyrolactone are likely to cause deterioration of the inkjet head, and the inkjet head is likely to be replaced frequently. Particularly in recent years, there has been a demand for a narrower frame of a display panel, and accordingly, the nozzle diameter of an inkjet head has become smaller. If the nozzle diameter becomes smaller, the ejection margin becomes narrower, which may cause deterioration of the inkjet head.

Demand for higher performance liquid crystal elements is also increasing. From these requirements, there is a demand for a high-quality liquid crystal element that suppresses a reduction in product yield by increasing the coating property of a liquid crystal aligning agent on a substrate and that hardly causes an afterimage even when the voltage application is released.

The present disclosure has been made in view of the above circumstances, and provides a liquid crystal aligning agent that has good coatability on a substrate, is less likely to deteriorate an inkjet head, and can obtain a liquid crystal element having excellent afterimage characteristics. Is the main purpose.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and include a liquid crystal aligning agent containing a compound in which a hydrogen atom bonded to a ring portion of an aromatic ring is substituted with a hydroxyalkyl group or an alkoxy group having 1 to 3 carbon atoms. It was found that the above problems can be solved by doing so. Specifically, according to the present disclosure, the following means are provided.
[1] A liquid crystal aligning agent containing a polymer component and a compound [A] represented by the following formula (1).
(R ² )x-Ar ¹ -R ¹ (1)
(In the formula (1), Ar ¹ is a (x+1)-valent aromatic ring group, and R ² is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And x is 0 or 1. R ¹ is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)
[2] A method for manufacturing a liquid crystal element including a liquid crystal alignment film, wherein the liquid crystal alignment film is formed using the liquid crystal alignment agent according to [1] above.
[3] A liquid crystal alignment film formed using the liquid crystal alignment agent according to the above [1].
[4] A liquid crystal device including the liquid crystal alignment film of [3].

According to the present disclosure, it is possible to provide a liquid crystal aligning agent that has good coatability on a substrate and that does not easily deteriorate an inkjet head. In addition, a liquid crystal element having excellent afterimage characteristics can be manufactured.

≪Liquid crystal aligning agent≫
The liquid crystal aligning agent of the present disclosure contains a polymer component and a solvent component. Below, each component contained in the liquid crystal aligning agent and other components optionally blended as necessary will be described.

<< Polymer component >>
As the polymer component contained in the liquid crystal aligning agent, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polymerizable Examples of the polymer include a polymer having a structural unit derived from a monomer having an unsaturated bond (hereinafter, also referred to as “polymer (Q)”) as a main skeleton. From the viewpoint of sufficiently ensuring the performance of the liquid crystal element, the polymer component contains at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyamide, and polymer (Q). It is preferable.

<Polyamic acid>
The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound.
(Tetracarboxylic acid dianhydride)
Examples of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and the like. .. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-Tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1 ,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-Oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 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, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) Diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4' -Diphenylsulfone tetracarboxylic dianhydride, 2,2'-dichloro-3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2'-dimethyl-3,3',4 4′-diphenylsulfone tetracarboxylic acid dianhydride and the like can be mentioned, respectively, and the tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(Diamine compound)
Examples of the diamine compound used for synthesizing the polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane and the like. Specific examples of these diamines include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine; and alicyclic diamines such as 1,4 -Diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc.;
Examples of aromatic diamines include dodecaneoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanooxy-2,4-diaminobenzene, pentadecanooxy-2,5-diamino. Benzene, octadecanooxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2, 4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6- Bis(4-aminophenoxy)cholestane, 2,4-diamino-N,N-diallylaniline, 4-(4′-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis( 4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid=5ξ-cholestan-3-yl, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, —O—, *—COO— or *—OCO— (where “*” is a bond to 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, and b is 0. Is an integer of 2 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b are not 0 at the same time.)
A compound represented by the following formula, a side chain type diamine such as a diamine having a cinnamic acid structure in its side chain:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1, 5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,10-bis(4-aminophenoxy)decane, 1,2-bis(4-aminophenyl) Ethane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,4-bis(4-aminophenylsulfanyl)butane, bis[2-(4-amino) Phenyl)ethyl]hexanedioic 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'-diaminobiphenyl, 4,4'-diamino Diphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4′-(phenylenediisopropylidene)bisaniline, 1, 4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-) Diyl)] dianiline, 4,4'-diaminobenzanilide, 4,4'-diaminostilbenzene, 4,4'-diaminodiphenylamine, 1,3-bis(4-aminophenethyl)urea, 1,3-bis( 4-aminobenzyl)urea, 1,4-bis(4-aminophenyl)-piperazine, N-(4-aminophenylethyl)-N-methylamine, N,N′-bis(4-aminophenyl)-N , N′-dimethylbenzidine and other main chain type diamines; and diaminoorganosiloxanes such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; 2010-9718 The diamine described in JP-A-8 can be used.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic acid dianhydride and a diamine compound together with a molecular weight modifier, if necessary. The ratio of the tetracarboxylic acid dianhydride and the diamine compound used for the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 with respect to 1 equivalent of the amino group of the diamine compound. A ratio of up to 2 equivalents is preferable. 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, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. Can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less based on 100 parts by mass of the total 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 to 24 hours.
Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols as a solvent, or a mixture of at least one of these with other organic solvents (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.) preferable. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 to 50% by mass with respect to the total amount (a+b) of the reaction solution. Is preferred. The reaction solution obtained by dissolving the polyamic acid may be directly used for preparing the liquid crystal aligning agent, or the polyamic acid contained in the reaction solution may be isolated and then used for preparing the liquid crystal aligning agent.

<Polyamic acid ester>
The polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine compound, [III] tetracarboxylic acid. It can be obtained by a method of reacting an acid diester dihalide with a diamine compound. The polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partial esterified product having both an amic acid structure and an amic acid ester structure. The reaction solution obtained by dissolving the polyamic acid ester may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. Good.

<Polyimide>
The polyimide can be obtained, for example, by subjecting the polyamic acid synthesized as described above to dehydration ring closure to imidize. The polyimide may be a complete imidized product obtained by dehydration ring closure of all of the amic acid structure of the precursor polyamic acid, dehydration ring closure of only a portion of the amic acid structure, amic acid structure and imide It may be a partial imidized product having a ring structure. The imidization ratio of the polyimide is preferably 20 to 99%, more preferably 30 to 90%. This imidization ratio is a percentage of the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method in which the polyamic acid is dissolved in an organic solvent, a dehydrating agent and a dehydration ring closure catalyst are added to this solution, and heating is carried out if necessary. In this method, as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. Examples of the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature for the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours. The reaction solution containing the polyimide may be used as it is for preparing the liquid crystal aligning agent, or may be used for preparing the liquid crystal aligning agent after isolating the polyimide. Polyimide can also be obtained by imidization of polyamic acid ester.

<Polyorganosiloxane>
The polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Examples of the silane compound include tetramethoxysilane, methyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyl. Examples thereof include dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and trimethoxysilylpropylsuccinic anhydride. The hydrolyzable silane compounds may be used alone or in combination of two or more. “(Meth)acryloxy” is meant to include “acryloxy” and “methacryloxy”.

The hydrolysis/condensation reaction is carried out by reacting one or more silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. In the reaction, the amount of water used is preferably 1 to 30 mol per 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 the catalyst used varies depending on the type of the catalyst, reaction conditions such as temperature, and the like, but is, for example, 0.01 to 3 times the mol of the total amount of the silane compound. Examples of the organic solvent used include hydrocarbons, ketones, esters, ethers, alcohols and the like, and it is preferable to use a water-insoluble or slightly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 to 10,000 parts by mass with respect to 100 parts by mass in total of the silane compound used in the reaction. The above reaction is preferably carried out by heating with an oil bath or the like. The heating temperature at that time is preferably 130° C. or lower, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the organic solvent layer separated from the reaction solution is dried with a desiccant, if necessary, and then the solvent is removed to obtain the target polyorganosiloxane. The method for synthesizing the polyorganosiloxane is not limited to the above hydrolysis/condensation reaction, and for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol may be used.

When a liquid crystal aligning agent contains a polyorganosiloxane having a side chain having a functional functional group such as a photo-alignment group or a pretilt angle imparting group, for example, an epoxy group-containing silane compound is used as at least a part of the raw material. A polyorganosiloxane having an epoxy group in a side chain is synthesized by polymerization, and then an epoxy group-containing polyorganosiloxane is reacted with a carboxylic acid having a functional functional group to obtain a target polyorganosiloxane. You can Alternatively, a method of polymerization using a hydrolyzable silane compound having a functional functional group as a monomer may be adopted.

<Polyamide>
Polyamide can be obtained by a method of reacting a dicarboxylic acid and a diamine compound, or the like. The dicarboxylic acid is preferably subjected to acid chloride formation using a suitable chlorinating agent such as thionyl chloride and then subjected to a reaction with a diamine compound.

The dicarboxylic acid used in the synthesis of the polyamide is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid and fumaric acid; cyclobutane. Alicyclic dicarboxylic acids such as dicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 2,5-dimethylterephthalic acid, 4-carboxycinnamic acid, Aromatic dicarboxylic acids such as 3,3′-[4,4′-(methylenedi-p-phenylene)]dipropionic acid and 4,4′-[4,4′-(oxydi-p-phenylene)]dibutyric acid And the like. Examples of the diamine compound used for the synthesis include the diamine compounds exemplified in the explanation of polyamic acid. The dicarboxylic acid and diamine compounds may each be used alone or in combination of two or more.

The reaction of the dicarboxylic acid and the diamine compound is preferably carried out in an organic solvent in the presence of a base. At this time, the use ratio of the dicarboxylic acid and the diamine compound is preferably such that the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine compound. The reaction temperature is preferably 0°C to 200°C, and the reaction time is preferably 0.5 to 48 hours. As the organic solvent, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used. As the base, for example, tertiary amines such as pyridine, triethylamine and N-ethyl-N,N-diisopropylamine can be preferably used. The amount of the base used is preferably 2 to 4 mol per 1 mol of the diamine compound. The solution obtained by the above reaction may be directly used for preparing the liquid crystal aligning agent, or may be used for preparing the liquid crystal aligning agent after isolating the polyamide contained in the reaction solution.

<Polymer (Q)>
Examples of the monomer having a polymerizable unsaturated bond include compounds having a (meth)acryloyl group, a vinyl group, a vinylphenyl group, a styryl group, a maleimide group and the like. Specific examples of such compounds include unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid and vinylbenzoic acid: alkyl (meth)acrylate, cycloalkyl (meth)acrylate. , Benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid Unsaturated carboxylic acid esters such as 3,4-epoxycyclohexylmethyl, (meth)acrylic acid 3,4-epoxybutyl, acrylic acid 4-hydroxybutyl glycidyl ether: Unsaturated polycarboxylic acid anhydrides such as maleic anhydride: (Meth)acrylic compounds such as styrene, methylstyrene, aromatic vinyl compounds such as divinylbenzene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; N-methylmaleimide, N -Maleimide group-containing compounds such as -cyclohexylmaleimide and N-phenylmaleimide; and the like. In addition, the monomer which has a polymerizable unsaturated bond can be used individually by 1 type or in combination of 2 or more types. In the present specification, “(meth)acrylic” is meant to include “acrylic” and “methacrylic”.

The polymer (Q) can be obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. Examples of the polymerization initiator used include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2) , 4-dimethylvaleronitrile) and the like are preferable. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of all the 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, hydrocarbon compounds and the like, with diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate being preferred. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 to 36 hours. The amount (a) of the organic solvent used is such that the total amount (b) of the monomers used in the reaction is 0.1 to 60 mass% with respect to the total amount (a+b) of the reaction solution. Is preferred. The polymer solution obtained by the above reaction may be directly used for the preparation of the liquid crystal aligning agent, or the polymer (Q) contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal aligning agent.

The polymer used for preparing the liquid crystal aligning agent preferably has a solution viscosity of 10 to 800 mPa·s, and more preferably 15 to 500 mPa·s, which is prepared and measured under the conditions described below. The solution viscosity (mPa·s) is a concentration of 10 mass prepared by using a good solvent for the polymer (γ-butyrolactone, N-methyl-2-pyrrolidone, etc. in the case of polyamic acid, polyamic acid ester and polyimide). % Polymer solution at 25° C. using an E-type rotational viscometer.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) can be appropriately selected according to the type of the polymer, but is preferably 1,000 to 500,000. Yes, and more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, and more preferably 5 or less. The polymer used for preparing the liquid crystal aligning agent may be one kind or a combination of two or more kinds.

The polymer component contained in the liquid crystal aligning agent is selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane, from the viewpoint of liquid crystal aligning property, affinity with liquid crystal, and mechanical strength. It is preferable that it contains at least one selected. It is particularly preferable that the polymer component contains at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester as a main component. Here, the main component is a component having the largest content on a mass basis, and for example, a component having a content of 50 mass% or more. That is, the polymer component, at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester, preferably contains 50% by mass or more, and 60% by mass or more based on the total amount of the polymer components. It is more preferable that the content is 80% by mass or more.

<<Compound [A]>>
The liquid crystal aligning agent of the present disclosure contains a compound [A] represented by the following formula (1).
(R ² )x-Ar ¹ -R ¹ (1)
(In the formula (1), Ar ¹ is a (x+1)-valent aromatic ring group, and R ² is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And x is 0 or 1. R ¹ is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)
By including the compound [A], the polymer component is uniformly dissolved in the solvent component, the wettability and spreadability when applied to the substrate are good, and deterioration of the resin member (inkjet head etc.) is less likely to occur. It can be a liquid crystal aligning agent.

In the above formula (1), the (x+1)-valent aromatic ring group of Ar ¹ is a group obtained by removing (x+1) hydrogen atoms from the ring portion of the aromatic ring. The aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocycle. Specific examples of the aromatic ring include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring and an anthracene ring; and an aromatic heterocycle such as a pyrrole ring, a pyridine ring, a pyrimidine ring and a pyridazine ring. Examples thereof include a ring, a furan ring, an oxygen-containing heterocycle such as an oxazole ring, and a sulfur-containing heterocycle such as a thiol ring and a thiazole ring. In addition, among the above, the oxazole ring and the thiazole ring are also nitrogen-containing heterocycles. Of these, Ar ¹ is preferably a group obtained by removing (x+1) hydrogen atoms from the ring portion of a benzene ring or a 5-membered heterocyclic ring, and (x+1) from the ring portion of a benzene ring or a furan ring. It is particularly preferable that it is a group in which the hydrogen atom of is removed.

Regarding R ¹ in the above formula (1), examples of the hydroxyalkyl group having 1 to 3 carbon atoms include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group and 2-hydroxypropyl group. , 3-hydroxypropyl group, and 2-hydroxy-1-methylethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group. R ¹ is preferably linear.
Regarding R ² , the alkyl group having 1 to 3 carbon atoms may be linear or branched, but is preferably linear. For specific examples in the case where R ² is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, the above description of R ¹ is applied. R ² is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
It is preferable that x is 0.

Compound [A] is a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3) It is particularly preferable that it is at least one selected from the group consisting of

(In the formulas (1-1) to (1-3), n and r are each independently an integer of 1 to 3, m is an integer of 0 to 2. R ³ is a carbon number of 1 to 3. Is an alkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and y is 0 or 1.)

In the above formulas (1-1) to (1-3), the description of the specific examples and preferred examples of R ² above applies to R ³ . The bonding position of R ³ is not particularly limited, but it is preferably ortho to the group “—(CH ₂ ) _n —OH” or the group “—O—(CH ₂ ) _m —CH ₃ ”. It is preferable that y is 0.

Preferred specific examples of the compound [A] include compounds represented by the following formulas (1-1-1) to (1-1-3) as the compounds represented by the above formula (1-1). As the compound represented by the above formula (1-2), compounds represented by the following formulas (1-2-1) to (1-2-4) are respectively represented by the above formula (1-3) Examples of the compound represented by are the compounds represented by the following formulas (1-3-1) to (1-3-6).

As the compound [A], among the compounds represented by the above formulas (1-1) to (1-3), compounds in which y=0 are preferable. Among these, the compounds represented by the above formulas (1-1-1) and (1-2-1) are preferable because they are more excellent in ink jet coatability, and are more resistant to deterioration of the ink jet head. Compounds represented by the above formulas (1-1-1) and (1-3-1) are preferable. As the compound [A], one type may be used alone, or two or more types may be used in combination.

The content ratio of the compound [A] is preferably 100 parts by mass or more, more preferably 300 parts by mass or more, and still more preferably 100 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the liquid crystal aligning agent. It is 600 parts by mass or more. The content ratio of the compound [A] is preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less.

Since the compound [A] has excellent solubility in the polymer component of the liquid crystal aligning agent, it is used as an alternative solvent for N-methyl-2-pyrrolidone (NMP) which is generally used as a good solvent for the polymer component. It is useful. In this case, the content ratio of NMP in the liquid crystal aligning agent is preferably 10 mass% or less, more preferably 5 mass% or less, and further preferably 1 mass% with respect to the total amount of the solvent component of the liquid crystal aligning agent. % Or less.

≪Other ingredients≫
The liquid crystal aligning agent may further contain a component different from the polymer component and the compound [A] (hereinafter, also referred to as “other component”), if necessary.

<Solvent [B]>
The liquid crystal aligning agent is an ether-based solvent, an alcohol-based solvent, a chain ester-based solvent, together with the polymer component and the compound [A], for the purpose of enhancing the wettability and spreading property of the liquid crystal aligning agent. And at least one solvent selected from the group consisting of ketone solvents (hereinafter, also referred to as “solvent [B]”).

Specific examples of the solvent [B] include ether solvents such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve). ), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, 3-methoxy-1-butanol, tetrahydrofuran, diisopentyl ether and the like;
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, 3-methoxy-3-methylbutanol, benzyl alcohol. As chain ester solvents, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl pro Peonate, isoamyl isobutyrate, etc.; as the ketone solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopentanone, 3-methylcyclohexanone, 4-methylcyclohexanone, diisobutyl ketone, etc., respectively. Can be mentioned.

As the solvent [B], at least one selected from the group consisting of ether solvents, alcohol solvents, and ketone solvents is preferable among the above, from the viewpoint that the effect of improving coatability can be further enhanced, and the solvent has 8 or less carbon atoms. At least one selected from the group consisting of ether solvents, alcohol solvents and cyclic ketone solvents is more preferable. Specifically, the solvent [B] is ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl. Particularly preferred is one selected from the group consisting of ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol and cyclopentanone. In addition, as a solvent [B], 1 type can be used individually or in combination of 2 or more types.

As the other component, the liquid crystal aligning agent is a solvent different from the solvent [B] (hereinafter, also referred to as "other solvent") for the purpose of further enhancing the solubility of the polymer component and the wettability and spreadability of the liquid crystal aligning agent. May be further included. Examples of the other solvent include aprotic polar solvents, halogenated hydrocarbon solvents, hydrocarbon solvents and the like. Specific examples of the other solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, gammabutyrolactone and propylene carbonate. , 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n- Butoxy-N-isopropyl-propionamide and the like; halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and the like; hydrocarbon solvents such as hexane , Heptane, octane, benzene, toluene, xylene and the like, respectively. Of the above solvents, the other solvent is preferably an aprotic polar solvent and is selected from the group consisting of gamma butyrolactone, N-ethyl-2-pyrrolidone, propylene carbonate, and 1,3-dimethyl-2-imidazolidinone. More preferably, it is at least one kind. In addition, as another solvent, 1 type can be used individually or in combination of 2 or more types.

The content ratio of the compound [A] is such that the solvent (compound [A], solvent [B]) contained in the liquid crystal aligning agent is suitably suppressed from the viewpoint of suitably suppressing deterioration of the inkjet head while improving the coating property of the liquid crystal aligning agent. And other solvents) is preferably 10% by mass or more. The content ratio is more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more, based on the total amount of the solvent. Further, the content ratio of the compound [A] is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the solvent contained in the liquid crystal aligning agent. Is.

When the liquid crystal aligning agent contains the solvent [B], the content ratio of the solvent [B] is preferably 5% by mass or more, and more preferably 10% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent. % Or more. Further, the content ratio of the solvent [B] is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less based on the total amount of the solvent of the liquid crystal aligning agent. The content ratio of the other solvent is preferably 80% by mass or less, more preferably 70% by mass or less, and 60% by mass or less with respect to the total amount of the solvent contained in the liquid crystal aligning agent. Is more preferable, and particularly preferably 50% by mass or less.

Other components that may be contained in the liquid crystal aligning agent include, in addition to the above components, for example, an epoxy group-containing compound (eg, N,N,N′,N′-tetraglycidyl-m-xylenediamine, N,N,N). ',N'-Tetraglycidyl-4,4'-diaminodiphenylmethane etc.), functional silane compounds (eg 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane etc.) ), an antioxidant, a metal chelate compound, a curing catalyst, a curing accelerator, a surfactant, a filler, a dispersant, and a photosensitizer. The mixing ratio of these additives can be appropriately selected according to each compound within a range that does not impair the effects of the present disclosure.

The ratio D of the components in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent other than the solvent is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 1 to 10% by mass. It is a range. When the ratio D is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the ratio D exceeds 10% by mass, the film thickness of the coating film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating property tends to deteriorate. It is in.

The reason why the use of the compound [A] made it possible to obtain the effect of suppressing the deterioration of the inkjet head while maintaining good coatability of the liquid crystal aligning agent on the substrate while maintaining good afterimage characteristics of the liquid crystal element. Although it is not clear, one of the reasons is due to the chemical structure of the compound [A], and more specifically, when the liquid crystal aligning agent is applied onto the substrate, the chemical structure of the compound [A] (the above It is assumed that the orientation of the liquid crystal was controlled to some extent due to the structure represented by the formula (1). However, this speculation does not limit the present disclosure.

<<Liquid crystal alignment film and liquid crystal element>>
The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The liquid crystal element can be effectively applied to various uses, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, various monitors, a liquid crystal television. , A display device such as an information display, a light control film, a retardation film, or the like. When used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited. For example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB. It can be applied to various operation modes such as (Optically Compensated Bend) type.

A method of manufacturing a liquid crystal element will be described by taking a liquid crystal display element as an example. The liquid crystal display element can be manufactured by, for example, a method including the following steps 1 to 3. In step 1, the substrate used differs depending on the desired operation mode. Steps 2 and 3 are common to each operation mode.

(Step 1: Formation of coating film)
First, a liquid crystal aligning agent is applied onto a substrate, and the applied surface is preferably heated to form a coating film on the substrate. As the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly(alicyclic olefin) can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Co., USA), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ). Etc. can be used. When manufacturing a TN type, STN type, or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, when manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with an electrode formed of a comb-shaped patterned transparent conductive film or a metal film, and a counter substrate provided with no electrode To use. As the metal film, a film made of a metal such as chromium can be used.

The coating of the liquid crystal aligning agent on the substrate is preferably performed by an offset printing method, a spin coating method, a roll coater method, a flexo printing method or an inkjet printing method on the electrode formation surface. In particular, the liquid crystal aligning agent has good wettability and spreadability, and in that it can suppress deterioration of the resin member constituting the inkjet head, excellent printability can be exhibited when the inkjet printing method is adopted, and product yield is improved. It is preferable in that the decrease can be suppressed and a liquid crystal alignment film having high performance can be obtained.

After applying the liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of preventing the liquid crystal aligning agent applied from dripping. The prebake temperature is preferably 30 to 200° C., and the prebake time is preferably 0.25 to 10 minutes. After that, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermal imidization of the amic acid structure of the polymer. The baking temperature (post bake temperature) is preferably 80 to 300° C., and the post bake time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm. After applying the liquid crystal aligning agent on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be the liquid crystal alignment film.

(Process 2: Alignment treatment)
When manufacturing a TN-type, STN-type, IPS-type or FFS-type liquid crystal display element, a treatment (alignment treatment) for imparting a liquid crystal aligning ability to the coating film formed in the above step 1 is carried out. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the orientation treatment, for example, a rubbing treatment of rubbing the coating film in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, or irradiating a coating film formed on a substrate with a liquid crystal aligning agent with light irradiation. A photo-alignment treatment for imparting a liquid crystal aligning ability to the coating film may be mentioned. On the other hand, in the case of producing a vertical alignment type liquid crystal device, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film is subjected to alignment treatment (rubbing treatment, optical alignment treatment). Etc.) may be given. The liquid crystal aligning agent suitable for the vertical alignment type liquid crystal display element can also be suitably used for the PSA (Polymer sustained alignment) type liquid crystal display element.

(Process 3: Construction of liquid crystal cell)
A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed as described above, and disposing the liquid crystal between the two substrates facing each other. In order to manufacture a liquid crystal cell, for example, (1) two substrates are arranged so as to face each other with a gap (spacer) so that the liquid crystal alignment films face each other, and the periphery of the two substrates is sealed with a sealant. A method of laminating and injecting liquid crystal into a cell gap defined by a substrate surface and a sealing agent and then sealing the injection hole, (2) sealing at a predetermined place on one substrate on which a liquid crystal alignment film is formed A method of applying an agent and further dropping liquid crystal at a predetermined number of points on the surface of the liquid crystal alignment film, and then bonding the other substrate so that the liquid crystal alignment film faces and spreading the liquid crystal over the entire surface of the substrate (ODF method). ) And the like. It is desirable that the produced liquid crystal cell is further heated to a temperature at which the liquid crystal used has an isotropic phase and then gradually cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal.

As the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as a spacer can be used. As the spacer, a photo spacer, a bead spacer, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable. In addition, a nematic liquid crystal or a smectic liquid crystal may be added with, for example, a cholesteric liquid crystal, a chiral agent, or a ferroelectric liquid crystal. In the case of manufacturing a PSA type liquid crystal display element, a polymerizable monomer is placed together with a liquid crystal between a pair of substrates, and a light irradiation is performed after a liquid crystal cell is constructed and a voltage is applied between the pair of electrodes.

Next, attach a polarizing plate to the outer surface of the liquid crystal cell if necessary. Examples of the polarizing plate include a polarizing film in which a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between cellulose acetate protective films, or a polarizing plate composed of the H film itself. Thus, a liquid crystal display device is obtained.

Hereinafter, the embodiments will be described in more detail based on examples, but the present disclosure is not limitedly interpreted by the following examples.

In the following examples, the weight average molecular weight Mw of the polymer, the imidization ratio of polyimide in the polymer solution, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods. The necessary amounts of the raw material compounds and polymers used in the following examples were secured by repeating the synthesis on the synthetic scale shown in the following synthesis examples as needed.

[Weight average molecular weight Mw of polymer]
The weight average molecular weight Mw is a polystyrene conversion value measured by GPC under the following conditions.
Column: Tosoh Corp., TSKgelGRCXLII
Solvent: Tetrahydrofuran, or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40°C
Pressure: 68 kgf/cm ²
[Imidization rate of polyimide]
The polyimide solution was poured into pure water, the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was calculated by the following mathematical formula (1).
Imidization rate [%]=(1-(A ¹ /(A ² ×α)))×100 (1)
(In Formula (1), A ¹ is a peak area derived from a proton of an NH group appearing in the vicinity of a chemical shift of 10 ppm, A ² is a peak area derived from another proton, and α is a precursor of a polymer (polyamic acid). The ratio of the number of other protons to one proton of the NH group in ).)
[Solution viscosity of polymer solution]
The solution viscosity (mPa·s) of the polymer solution was measured at 25° C. using an E-type rotational viscometer.
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

The compound abbreviations are as follows. In the following, the compound represented by the formula (X) may be simply referred to as “compound (X)”.

・Tetracarboxylic dianhydride and diamine compound

・Compound [A]

<Synthesis of polymer>
[Synthesis Example 1: Synthesis of Polyimide (PI-1)]
22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as tetracarboxylic dianhydride, and 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine ), and 10.5 g (0.02 mol) of cholestanil 3,5-diaminobenzoate are dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60° C. for 6 hours to give polyamic acid of 20%. A solution containing mass% was obtained. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa·s.
Next, NMP was added to the obtained polyamic acid solution to obtain a solution having a polyamic acid concentration of 7% by mass, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110° C. for 4 hours. .. After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP (the pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system by this operation. The same applies hereinafter), and the imidization ratio was about 68. A solution containing 26% by weight of polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 45 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-1).

[Synthesis Example 2: Synthesis of Polyimide (PI-2)]
As tetracarboxylic dianhydride, TCA 110 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho 160 g (0.50 mol) of [1,2-c]furan-1,3-dione, 91 g (0.85 mol) of PDA as a diamine, 25 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane ( 0.10 mol), and 25 g (0.040 mol) of 3,6-bis(4-aminobenzoyloxy)cholestane and 1.4 g (0.015 mol) of aniline as a monoamine were dissolved in 960 g of NMP, and the mixture was mixed at 60° C. By carrying out the reaction for 6 hours, a solution containing a polyamic acid was obtained. A small amount of the obtained polyamic acid solution was sampled, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 60 mPa·s.
Next, 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone (GBL) to obtain about 2,500 g of a solution containing 15% by mass of polyimide (PI-2) having an imidization ratio of about 95%. Obtained. A small amount of this solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 70 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-2).

[Synthesis Example 3: Synthesis of Polyimide (PI-3)]
As in Synthesis Example 1 above, except that the diamine used was changed to 0.08 mol of 3,5-diaminobenzoic acid (compound (DA-12)) and 0.02 mol of cholestanyloxy-2,4-diaminobenzene. A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 80 mPa·s. Then, imidization was carried out by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-3) having an imidization ratio of about 65%. A small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 40 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-3).

[Synthesis Example 4: Synthesis of Polyimide (PI-4)]
The tetracarboxylic acid dianhydride used was 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride 0.04 mol, and pyromellitic acid. Same as Synthesis Example 1 except that the dianhydride was changed to 0.02 mol and the diamine used was changed to 0.06 mol of the compound (DA-2) and 0.04 mol of the compound (DA-1). A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 mass% was 75 mPa·s. Then, imidization was performed in the same manner as in Synthesis Example 1 above to obtain a solution containing 26% by mass of polyimide (PI-4) having an imidization ratio of about 50%. A small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 40 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-4).

[Synthesis Example 5: Synthesis of Polyimide (PI-5)]
The tetracarboxylic dianhydride used was changed to 0.08 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 0.02 mol of pyromellitic dianhydride, and the diamine used was 4-Aminophenyl-4-aminobenzoate (Compound (DA-3)) 0.098 mol and Compound (DA-4) 0.002 mol except that the polyamic acid was prepared in the same manner as in Synthesis Example 1 above. A solution was obtained. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 80 mPa·s. Then, imidization was carried out by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-5) having an imidization ratio of about 65%. A small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 50 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyimide (PI-5).

[Synthesis Example 6: Synthesis of polyamic acid (PA-1)]
1,2,3,4-Cyclobutane tetracarboxylic dianhydride (CB) 200 g (1.0 mol) as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4'-diaminobiphenyl 210 g as diamine (1.0 mol) was dissolved in a mixed solvent of 370 g of NMP and 3,300 g of γ-butyrolactone (GBL) and reacted at 40° C. for 3 hours to give a polyamic acid having a solid content concentration of 10% by mass and a solution viscosity of 160 mPa·s. A solution was obtained. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-1).

[Synthesis Example 7: Synthesis of polyamic acid (PA-2)]
As tetracarboxylic dianhydride, 7.0 g (0.031 mol) of TCA and 13 g of compound (DA-5) as diamine (corresponding to 1 mol per 1 mol of TCA) were dissolved in 80 g of NMP, and the mixture was mixed at 60° C. for 4 hours. By carrying out the reaction for time, a solution containing 20% by mass of polyamic acid (PA-2) was obtained. The solution viscosity of this polyamic acid solution was 2,000 mPa·s. The compound (DA-5) was synthesized according to the description in JP-A-2011-10099. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-2).

[Synthesis Example 8: Synthesis of polyamic acid (PA-3)]
The above synthetic example except that the diamine used was changed to 0.7 mol of 1,3-bis(4-aminophenethyl)urea (compound (DA-6)) and 0.3 mol of compound (DA-7). A polyamic acid solution was obtained in the same manner as in 6. A small amount of the obtained polyamic acid solution was sampled, NMP was added thereto, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 mass% was 100 mPa·s. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-3).

[Synthesis Example 9: Synthesis of polyamic acid (PA-4)]
The tetracarboxylic acid dianhydride used was changed to 1.0 mol of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and the diamine used was p-phenylenediamine 0. Synthetic Example 6 above except that the amount was changed to 0.3 mol, the compound (DA-7) 0.2 mol, and 1,2-bis(4-aminophenoxy)ethane (compound (DA-9)) 0.5 mol. A polyamic acid solution was obtained by the same method as described above. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa·s. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-4).

[Synthesis Example 10: Synthesis of polyamic acid (PA-5)]
Diamine used was changed to 0.2 mol of 2,4-diamino-N,N-diallylaniline, 0.2 mol of 4,4′-diaminodiphenylamine, and 0.6 mol of 4,4′-diaminodiphenylmethane. In the same manner as in Synthesis Example 6 above, a polyamic acid solution was obtained. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 95 mPa·s. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-5).

[Synthesis Example 11: Synthesis of polyamic acid (PA-6)]
The tetracarboxylic dianhydride used was compounded with 0.2 mol of the compound (TA-1) and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8- The diamine was changed to 0.8 mol, and the diamine used was 0.4 mol of 3,5-diaminobenzoic acid, 0.25 mol of compound (DA-11), and 0.35 compound (DA-1). A polyamic acid solution was obtained in the same manner as in Synthesis Example 6 except that the molar amount was changed. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 mass% was 85 mPa·s. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain polyamic acid (PA-6).

[Synthesis Example 12: Synthesis of polyamic acid ester (PAE-1)]
0.035 mol of 2,4-bis(methoxycarbonyl)-1,3-dimethylcyclobutane-1,3-dicarboxylic acid was added to 20 ml of thionyl chloride, N,N-dimethylformamide was added in a catalytic amount, and then the mixture was heated to 80°C. And stirred for 1 hour. Then, the reaction solution was concentrated, and the residue was dissolved in 113 g of γ-butyrolactone (GBL) (this solution was referred to as reaction solution A). Separately, 0.01 mol of p-phenylenediamine, 0.01 mol of 1,2-bis(4-aminophenoxy)ethane, and 0.014 mol of compound (DA-8) were added to 6.9 g of pyridine, 44.5 g of NMP and GBL33. 0.5 g was added and dissolved, and this was cooled to 0°C. Then, the reaction solution A was slowly added dropwise to this solution over 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 4 hours. The obtained solution of polyamic acid ester was added dropwise to 800 ml of pure water while stirring, and the deposited precipitate was filtered. Subsequently, the polymer powder was washed 5 times with 400 ml of isopropyl alcohol (IPA) and dried to obtain 15.5 g of polymer powder. The weight average molecular weight Mw of the obtained polyamic acid ester (PAE-1) was 34,000.

[Synthesis Example 13: Synthesis of polyorganosiloxane (APS-1)]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (100.0 g), methylisobutylketone (500 g) and triethylamine (10.0 g) at room temperature. Mixed in. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then the reaction was carried out at 80° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a reactive polyorganosiloxane. (EPS-1) was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed on this reactive polyorganosiloxane (EPS-1), a peak based on an epoxy group was obtained in the vicinity of the chemical shift (δ)=3.2 ppm according to the theoretical intensity, and during the reaction, It was confirmed that the side reaction of the epoxy group did not occur. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500 and the epoxy equivalent was 180 g/mol.
Then, in a 200 mL three-necked flask, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-(dodecyloxy)benzoic acid as a reactive compound, and a catalyst. Was charged with 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.), and the reaction was carried out at 100° C. for 48 hours with stirring. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed 3 times with water, the organic layer was dried over magnesium sulfate, and the solvent was distilled off to give a liquid crystal aligning polyorganosiloxane (APS- 9.0 g of 1) was obtained. The weight average molecular weight Mw of the obtained polymer was 9,900.

<Preparation and evaluation of liquid crystal aligning agent>
[Example 1]
1. Preparation of Liquid Crystal Alignment Agent To the polyimide (PI-1) obtained in Synthesis Example 1 above, 3-phenylpropan-1-ol (compound a), γ-butyrolactone (γBL) and butylcellosolve (BC) were added to prepare a polymer. A solution having a concentration of 3.5% by mass and a solvent mixing ratio of compound a:γBL:BC=40:30:30 (mass ratio) was prepared. After sufficiently stirring this solution, a liquid crystal aligning agent (S-1) was prepared by filtering with a filter having a pore size of 0.2 μm. The liquid crystal aligning agent (S-1) is mainly used for manufacturing a vertical alignment type liquid crystal display element.

2. Evaluation of Inkjet Coating Property As a substrate on which the liquid crystal aligning agent is coated, a glass substrate with a transparent electrode made of ITO is heated on a hot plate at 200° C. for 1 minute, and then UV/ozone cleaning is performed to remove water on the transparent electrode surface. The one immediately after the contact angle was set to 10° or less was used. On this substrate, the above 1. The liquid crystal aligning agent (S-1) prepared in (3) was applied on the transparent electrode surface of the above-mentioned glass substrate with a transparent electrode using an inkjet coating machine (manufactured by Shibaura Mechatronics Co., Ltd.). At this time, the coating conditions were 2,500 times/(nozzle/minute) and two reciprocations (total 4 times) with a discharge amount of 250 mg/10 seconds. After the coating was allowed to stand for 1 minute, the substrate was heated at 50° C. to form a coating film having an average film thickness of 0.1 μm. The obtained coating film was visually observed under irradiation of an interference fringe measurement lamp (sodium lamp) to evaluate unevenness and cissing.
Further, the same operation as above was performed except that the heating temperature at the time of forming the coating film was changed from 50° C. to 60° C. and 80° C., and the presence or absence of unevenness and cissing of the coating film was observed. When neither unevenness nor cissing was observed at any heating temperature of 50° C., 60° C. and 80° C., the ink jet coatability was “good A (⊚)”, and one of 50° C., 60° C. and 80° C. When at least one of unevenness and cissing is observed at the heating temperature, "Good B (○)" is given. When at least one of unevenness and cissing is seen at two heating temperatures, "Available (△)" is given and all heating is performed. When at least one of unevenness and cissing was observed at the temperature, it was determined as "poor (x)". As a result, this example was evaluated as "good B".

3. Evaluation of long-term stability of inkjet head The effect of the liquid crystal aligning agent on the inkjet head was evaluated by evaluating the long-term stability of the inkjet head by the following method. For evaluation, a KM1024i matecon kit manufactured by Konica Minolta was used. Note that the material management kit is a sample piece for testing the solvent resistance of the inkjet head constituent member. Here, a resin cured product was used for the test among a plurality of sample pieces.
First, after confirming the color and surface state of the sample piece, the mass of the sample piece (weight W1 before immersion) was measured. Next, 100 ml of the solvent (compound a:γBL:BC=40:30:30 (mass ratio)) used for the preparation of the liquid crystal aligning agent was weighed in a sealable glass bottle, and the sample piece was dipped at 50° C. Stored for 4 weeks. After 4 weeks, the sample piece was taken out of the glass bottle, the solvent adhering to the surface of the sample piece was removed by air blow, and then the color change, the presence or absence of cracks, and the presence or absence of dissolution were visually confirmed. The change was evaluated. The evaluation was performed as follows.
-Regarding color change: When there is no color change, it is "good (○)", when the color changes slightly, it is "good (△)", and when the color changes significantly, it is "poor (x)" ..
-Presence or absence of cracks: When no cracks occurred, the result was "good", and when cracks occurred, the result was "bad".
-Regarding the presence or absence of dissolution: When dissolution of the resin was not confirmed by palpation, "good (○)" was set, and when dissolution was observed, "bad (x)" was set.
Further, the mass of the sample piece after the sample piece was immersed in the solvent (mass W2 after immersion) was measured, and the mass ratio α increased from the mass W1 before immersion was calculated by the following mathematical expression (2).
α [%]=((W2-W1)/W1)×100 (2)
The evaluation was “good A (⊚)” when the ratio α was less than 10%, “good B (◯)” when 10% or more and less than 30%, and 30% or more and less than 50%. In each case, it was evaluated as “Fair (Δ)” and when it was 50% or more, it was evaluated as “Poor (X)”. It should be noted that the lower the ratio α, the better the solvent to be evaluated is because it is less likely to swell the inkjet head constituent member. As a result of the evaluation, in this example, the color change was “good”, the presence or absence of cracks was “good”, the presence or absence of dissolution was “good”, and the mass change was “good”.

4. Manufacture of Vertical Alignment Type Liquid Crystal Display Device A liquid crystal aligning agent (S-1) was applied onto a glass substrate with a transparent electrode consisting of a pair (two sheets) of ITO film using a spinner, and prebaked for 1 minute on a hot plate at 80° C. I went. Then, the solvent was removed by heating (post-baking) at 200° C. for 1 hour in an oven purged with nitrogen to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 μm. The coating film was rubbed by a rubbing machine having a roll around which a rayon cloth was wound, with a roll rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a foot pressing length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film. Note that this rubbing treatment is a weak rubbing treatment performed for the purpose of controlling the collapse of the liquid crystal and performing alignment division by a simple method.
An epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was applied by screen printing to the outer periphery of the surface of one of the substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other. Then, they were overlapped and pressure-bonded, and heated at 150° C. for 1 hour to thermally cure the adhesive. Next, after filling a negative liquid crystal (MLC-6608 made by Merck) into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive to remove the flow alignment at the time of liquid crystal injection. This was heated at 150° C. for 10 minutes and then gradually cooled to room temperature. Further, a liquid crystal display element was manufactured by bonding two polarizing plates on both outer sides of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.

5. 4. Evaluation of variation characteristic of pretilt angle with respect to temperature unevenness of postbake (postbake margin) The pretilt angle of the liquid crystal display device obtained by forming the liquid crystal alignment film at different post-baking temperatures (120° C., 180° C. and 230° C.) was measured according to the method of 1. The measured value when the post-baking temperature was 230° C. was set as the reference pretilt angle θp, and the difference Δθ (=|θp−θa|) between the reference pretilt angle θp and the measured value θa indicates the pretilt angle with respect to the temperature unevenness of the post-bake. The variation characteristics were evaluated. It can be said that the smaller Δθ is, the smaller the variation in the pretilt angle with respect to the temperature unevenness is, and the better. The measurement of the pretilt angle is based on a method described in a non-patent document (T. J. Scheffer et. al. J. Appl. Phys. vo. 19, p. 2013 (1980)), and He-Ne laser light is used. The value of the tilt angle of the liquid crystal molecule from the substrate surface measured by the crystal rotation method using was used as the pretilt angle [°]. The evaluation is “good (◯)” when Δθ is 0.2° or less, “good (Δ)” and 0.5° when larger than 0.2° and less than 0.5°. The case where it was above was regarded as “poor (x)”. As a result, in this example, when the post-baking temperature was 180° C., the post-baking margin was “good”, and when it was 120° C., the evaluation was “good”.

6. Evaluation of AC afterimage characteristics Except for the point that the electrode structure was two-system ITO electrodes (electrode 1 and electrode 2) capable of independently switching application/non-application of voltage, and that a polarizing plate was not attached 4. A liquid crystal cell for evaluation was produced by the same method as described above. The liquid crystal cell for evaluation was placed under the condition of 60° C., and an alternating voltage of 10 V was applied to the electrode 1 for 300 hours without applying a voltage to the electrode 2. Immediately after 300 hours had elapsed, a voltage of AC 3V was applied to both the electrode 1 and the electrode 2, and the difference ΔT [%] in light transmittance between the electrodes was measured. At this time, when the ΔT is less than 2%, the AC afterimage characteristic is “good (◯)”, when it is 2% or more and less than 3%, it is “OK”, and when it is 3% or more, it is “good”. It was evaluated as "poor (x)". As a result, this example was evaluated as “good”.

7. Evaluation of DC afterimage characteristic 6. The evaluation liquid crystal cell prepared in 1. was placed under the condition of 60° C., a voltage of DC 0.5 V was applied to the electrode 1 for 24 hours, and the voltage (residual DC voltage) remaining on the electrode 1 immediately after the DC voltage was cut off was measured. It was determined by the flicker elimination method. At this time, when the residual DC voltage is less than 100 mV, the DC afterimage characteristic is “good (◯)”, when it is 100 mV or more and less than 300 mV is “OK”, and when it is 300 mV or more is “poor ( X)" was evaluated. As a result, this example was evaluated as “good”.

[Examples 2 to 9 and Comparative Examples 1 to 10]
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the compounding formulations were as shown in Table 1 below. Further, various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal aligning agent. The evaluation results are shown in Table 2 below.

[Example 10]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-10) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below. The liquid crystal aligning agent (S-10) is mainly used for manufacturing a horizontal alignment type liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-10) was used. The results are shown in Table 2 below.

3. Manufacture of a rubbing FFS type liquid crystal display element A glass substrate in which a flat plate electrode (bottom electrode), an insulating layer and a comb-teeth-shaped electrode (top electrode) are laminated in this order on one surface, and a counter glass substrate in which no electrode is provided The liquid crystal aligning agent (S-10) was applied onto each surface using a spinner, and heated (prebaked) on a hot plate at 80° C. for 1 minute. Then, it was dried (post-baked) for 1 hour in an oven at 200° C. in which the inside of the chamber was replaced with nitrogen to form a coating film having an average film thickness of 0.08 μm. Then, the surface of the coating film was rubbed with a rubbing machine having a roll around which a rayon cloth was wound, at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm/sec, and a foot pressing length of 0.4 mm. After that, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film.
Then, with respect to the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm was applied by screen printing, leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film was formed. Then, the substrates were superposed and pressure-bonded, and the adhesive was thermoset at 150° C. for 1 hour. Next, nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) was filled between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting liquid crystal, this was heated at 120° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell. When the pair of substrates were stacked, the rubbing directions of the substrates were antiparallel. In addition, the polarizing plates were attached so that the polarization directions of the two polarizing plates were parallel and orthogonal to the rubbing direction. Regarding the top electrodes, the line width of the electrodes was 4 μm and the distance between the electrodes was 6 μm. In addition, as the top electrodes, four-system drive electrodes of electrode A, electrode B, electrode C, and electrode D were used. In this case, the bottom electrode acts as a common electrode that acts on all the four-system drive electrodes, and each of the four-system drive electrode regions becomes a pixel region.
4. Evaluation of rubbing FFS type liquid crystal display device The post-bake margin, the AC afterimage characteristic and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the rubbing FFS type liquid crystal display element or the liquid crystal cell manufactured according to the method of 1. was used. The results are shown in Table 2 below.

[Examples 11 and 12]
Liquid crystal aligning agents (S-11) and (S-12) were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. Further, the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agents (S-11) and (S-12) were used, respectively, and the same as in Example 10. Then, a rubbing FFS type liquid crystal display element or liquid crystal cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.

[Example 13]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-13) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below. The liquid crystal aligning agent (S-13) is mainly used for manufacturing a PSA type liquid crystal display device.
2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-13) was used. The results are shown in Table 2 below.

3. Preparation of Liquid Crystal Composition 5% by mass of a liquid crystal compound represented by the following formula (L1-1) is represented by 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.), and represented by the following formula (L2-1). A liquid crystal composition LC1 was obtained by adding 0.3% by mass of a photopolymerizable compound described above and mixing them.

4. Production of PSA type liquid crystal display device A liquid crystal alignment film was formed in the same manner as in the method described in "4. Production of vertical alignment type liquid crystal display device" of Example 1 except that the liquid crystal aligning agent (S-13) was used. A pair (two) of substrates having the above-mentioned materials were obtained. Then, a liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal composition LC1 prepared above was used instead of MLC-6608, and that no polarizing plate was attached. Next, with the liquid crystal cell obtained above, an alternating current of 10 V with a frequency of 60 Hz was applied between the electrodes, and while the liquid crystal was driven, an ultraviolet irradiation device using a metal halide lamp as a light source was used to emit 50 Irradiation was performed at an irradiation dose of 000 J/m ² . It should be noted that this irradiation amount is a value measured using a photometer that measures the wavelength at 365 nm as a reference. Further, a liquid crystal display element was manufactured by bonding two polarizing plates on both outer sides of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.
5. Evaluation of PSA type liquid crystal display device The post-bake margin, the AC afterimage characteristic, and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the PSA type liquid crystal display element or the liquid crystal cell produced according to the method described in 1. was used. The results are shown in Table 2 below.

[Examples 14, 15, 25, 27]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. In addition, inkjet coating properties and long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that each liquid crystal aligning agent was used, and in the same manner as in Example 14, a PSA type liquid crystal display element or liquid crystal cell. Was manufactured and various evaluations were performed. The results are shown in Table 2 below.

[Example 16]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-16) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below. The liquid crystal aligning agent (S-16) is mainly used for manufacturing an optical vertical alignment type liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-16) was used. The results are shown in Table 2 below.

3. Manufacture of Vertically Aligned Liquid Crystal Display Device A liquid crystal aligning agent (S-16) was used, and instead of the rubbing treatment, the film was irradiated with polarized ultraviolet rays using a Hg-Xe lamp and a Glan-Taylor prism. An optical vertical alignment type liquid crystal display element was manufactured in the same manner as in the method described in "4. Manufacturing of vertical alignment type liquid crystal display element" of Example 1. The polarized ultraviolet rays were irradiated from a direction inclined by 40° from the substrate normal, the irradiation amount was 200 J/m ² , and the polarization direction was p-polarized light. This irradiation amount is a value measured using a photometer that measures the wavelength at 313 nm.
4. Evaluation of vertically aligned liquid crystal display device 3. The post-bake margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the liquid crystal display device or liquid crystal cell of the optical vertical alignment type manufactured according to the method described in 1 above was used. The results are shown in Table 2 below.

[Examples 17 and 18]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. In addition, the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that each liquid crystal aligning agent was used. A liquid crystal cell was manufactured and post-bake margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated. The results are shown in Table 2 below.

[Example 19]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-19) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below. The liquid crystal aligning agent (S-19) is mainly used for manufacturing an optical horizontal type liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-19) was used. The results are shown in Table 2 below.

3. Manufacture of optical FFS type liquid crystal display element In addition to using a liquid crystal aligning agent (S-19) and performing rubbing treatment, the film was irradiated with polarized ultraviolet rays using a Hg-Xe lamp and a Glan-Taylor prism. An optical FFS type liquid crystal display element was produced in the same manner as in the method described in “3. Production of rubbing FFS type liquid crystal display element” in Example 10. Irradiation of polarized ultraviolet rays was performed from a direction perpendicular to the substrate, the irradiation amount was 10,000 J/m ² , and the polarization direction was orthogonal to the rubbing direction in Example 10. This irradiation amount is a value measured using a photometer that measures the wavelength at 254 nm.
4. Evaluation of optical FFS type liquid crystal display device The post-bake margin, the AC afterimage characteristic, and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the optical FFS type liquid crystal display element or the liquid crystal cell manufactured according to the method described in 1. was used. The results are shown in Table 2 below.

[Examples 20 to 24]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the compounding formulation was changed as shown in Table 1 below. Further, the inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that each liquid crystal aligning agent was used, and in the same manner as in Example 21, an optical FFS type liquid crystal display element or liquid crystal was used. The cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.

[Example 26]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-26) was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1 below. The liquid crystal aligning agent (S-26) is mainly used for manufacturing a TN mode type liquid crystal display device.
2. Evaluation of Liquid Crystal Alignment Agent The inkjet coatability and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-26) was used. The results are shown in Table 2 below.

3. Manufacture of TN type liquid crystal display device Using a liquid crystal aligning agent (S-26), rubbing treatment was performed by a rubbing machine having a roll around which rayon cloth was wound, roll rotation speed was 500 rpm, stage moving speed was 3 cm/sec, and hair was pressed. A pair of substrates (two sheets) having a liquid crystal alignment film was prepared in the same manner as in the method described in "4. Manufacture of vertical alignment type liquid crystal display element" of Example 1 except that the condition was 0.4 mm in length. Obtained. Next, in place of MLC-6608, a positive type liquid crystal (MLC-6221 manufactured by Merck) was used so that the rubbing directions of the substrates were orthogonal to each other when the pair of substrates were stacked. A TN type liquid crystal display device was manufactured in the same manner as in Example 1 except that the polarization direction was parallel to the rubbing direction of each substrate.
4. Evaluation of TN type liquid crystal display device The post-bake margin, the AC afterimage characteristic, and the DC afterimage characteristic were evaluated in the same manner as in Example 1 except that the TN type liquid crystal display element or the liquid crystal cell manufactured according to the method described in 1. was used. The results are shown in Table 2 below.

In Table 1, the numerical value of the polymer component indicates the blending ratio (parts by mass) of each polymer to 100 parts by mass in total of the polymer components used for preparing the liquid crystal aligning agent. The numerical value of the solvent composition indicates the compounding ratio (mass ratio) of each compound to the total amount of the solvent (compound [A], solvent [B] and other solvent) used for the preparation of the liquid crystal aligning agent. The compound abbreviations are as follows.
(Compound [A])
a: 3-phenylpropan-1-ol b: 2-phenylethane-1-ol c: phenylmethanol d: anisole e: ethoxybenzene f: propoxybenzene g: 2-furanylmethanol h: 2-furanylethanol i : 2-furanyl propanol (solvent [B] and other solvents)
L: propylene carbonate m: 4-phenylbutan-1-ol n: butoxybenzene o: 2-furanylbutanol p: γ-butyrolactone q: dimethylimidazolidinone r: N-methyl-2-pyrrolidone s: butylcellosolve t: Diacetone alcohol u: Diethylene glycol diethyl ether v: N-ethyl-2-pyrrolidone w: Phenol x: Phenyl acetate

As can be seen from Table 2, in Examples 1 to 27 containing the compound [A], various properties such as inkjet coating property, inkjet head long-term stability, post bake margin, and afterimage property were improved in a well-balanced manner. On the other hand, in the examples (Comparative Examples 1 to 3 and 8 to 9) not containing the compound [A] but containing NMP, γ-butyrolactone, dimethylimidazolidinone, phenol and phenyl acetate, the inkjet head was stable for a long time. The sex was inferior to the example. In addition, in the examples (Comparative Examples 4 to 7) which did not contain the compound [A] but instead contained propylene carbonate, 4-phenylbutan-1-ol, butoxybenzene, and 2-furanylbutanol, the inkjet coatability was improved. It was inferior to the example.

From the above results, it has been clarified that the liquid crystal aligning agent containing the compound [A] has a good coating property on the substrate, does not easily deteriorate the inkjet head, and can obtain a liquid crystal element having excellent afterimage characteristics. It was Further, it was revealed that the liquid crystal aligning agent can also improve the post-baking margin.

Claims (8)

1. A liquid crystal aligning agent comprising a polymer component and a compound [A] represented by the following formula (1).
   (R ² )x-Ar ¹ -R ¹ (1)
   (In the formula (1), Ar ¹ is a (x+1)-valent aromatic ring group, and R ² is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And x is 0 or 1. R ¹ is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)
2. The compound [A] is selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3). The liquid crystal aligning agent according to claim 1, which is at least one selected.
   

   

   (In the formulas (1-1) to (1-3), n and r are each independently an integer of 1 to 3, m is an integer of 0 to 2. R ³ is a carbon number of 1 to 3. Is an alkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and y is 0 or 1.)
3. The liquid crystal aligning agent according to claim 1 or 2, which contains at least one solvent [B] selected from the group consisting of an ether solvent, an alcohol solvent, a chain ester solvent, and a ketone solvent.
4. The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the content ratio of the compound [A] is 10% by mass or more based on the total amount of the solvent contained in the liquid crystal aligning agent.
5. As the polymer component, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyamide, and at least one selected from the group consisting of a polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond, The liquid crystal aligning agent according to any one of claims 1 to 4.
6. A method of manufacturing a liquid crystal device including a liquid crystal alignment film,
   A method for manufacturing a liquid crystal element, comprising forming the liquid crystal alignment film using the liquid crystal alignment agent according to claim 1.
7. A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of claims 1 to 5.
8. A liquid crystal device comprising the liquid crystal alignment film according to claim 7.