TWI819102B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method thereof - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent that has good coating properties on a substrate, is difficult to cause deterioration of an inkjet head, and can obtain a liquid crystal element with excellent afterimage characteristics. The liquid crystal alignment agent contains a polymer component and a compound [A] represented by the following formula (1).

(R ² )x-Ar ¹ -R ¹ ...(1)

(In formula (1), Ar ¹ is an aromatic ring group with a valence of (x+1), and R ² is an alkyl group with 1 to 3 carbon atoms, a hydroxyalkyl group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms. Oxygen group, x is 0 or 1. R ¹ is a hydroxyalkyl group with 1 to 3 carbon atoms or an alkoxy group with 1 to 3 carbon atoms)

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing thereof method

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

The liquid crystal element has a liquid crystal alignment film that has the function of aligning liquid crystal molecules in a liquid crystal layer in a certain direction. Generally, the liquid crystal alignment film is formed by coating a liquid crystal alignment agent obtained by dissolving a polymer component in an organic solvent on the surface of a substrate, and preferably by heating the film. As the solvent component of the liquid crystal alignment agent, N-methyl-2-pyrrolidone or γ-butyrolactone or the like is usually used as a solvent with high solubility (good solvent) for the polymer component. In addition, by mixing and using a solvent (poor solvent) with low solubility of polymer components such as butyl cellosolve and these good solvents, the wettability and spreadability to the substrate is improved (see, for example, Patent Document 1 or patent document 2).

In recent years, the increase in the size of liquid crystal display devices has been achieved by increasing the size of the substrate using a large production line, or by obtaining multiple panels from one substrate to reduce the time and cost of the manufacturing steps. On the other hand, if the substrate is enlarged, the coating area of the liquid crystal alignment agent becomes large, so it is difficult to ensure uniformity of film quality over the entire coating area. In order to eliminate this coating problem In recent years, a coating method using inkjet printing has been introduced into the manufacturing process of large-scale liquid crystal panels.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2017-198975

[Patent Document 2] Japanese Patent Application Publication No. 2016-206645

Since the polymer component of the liquid crystal alignment agent has excellent solubility, N-methyl-2-pyrrolidone or γ-butyrolactone is used to coat the liquid crystal alignment agent on the liquid crystal alignment agent by inkjet printing when manufacturing large liquid crystal panels. In the case of a substrate, uneven coating of the liquid crystal alignment agent can be reduced. On the other hand, N-methyl-2-pyrrolidinone or γ-butyrolactone tends to cause deterioration of the inkjet head, and the frequency of replacement of the inkjet head tends to increase. In particular, in recent years, display panels have been required to have narrow bezels, and with this, the nozzle diameter of the inkjet head has become smaller. If the nozzle diameter becomes smaller, the ejection margin becomes narrower, which may cause deterioration of the inkjet head more easily.

In addition, the demand for higher performance of liquid crystal elements is further increasing. In response to such demands, a high-quality liquid crystal element is required that suppresses a decrease in product yield by improving the coating properties of a liquid crystal alignment agent on a substrate and is less likely to produce residual images even when voltage application is removed.

The present invention was made in view of the above situation, and its main purpose is to provide a method that has good coating properties on a substrate, is difficult to cause deterioration of the inkjet head, and can obtain afterimage characteristics. Excellent liquid crystal alignment agent for liquid crystal elements.

The inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and found that by making the liquid crystal alignment agent contain a hydrogen atom bonded to the ring portion of the aromatic ring via a hydroxyalkyl group or alkyl group having 1 to 3 carbon atoms, Compounds substituted with oxygen groups can solve the above problems. Specifically, according to the present invention, the following means are provided.

[1] A liquid crystal alignment agent containing a polymer component and a compound [A] represented by the following formula (1).

(R ² )x-Ar ¹ -R ¹ ...(1)

(In formula (1), Ar ¹ is an aromatic ring group with a valence of (x+1), and R ² is an alkyl group with 1 to 3 carbon atoms, a hydroxyalkyl group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms. Oxygen group, x is 0 or 1. R ¹ is a hydroxyalkyl group with 1 to 3 carbon atoms or an alkoxy group with 1 to 3 carbon atoms)

[2] A method of manufacturing a liquid crystal element, which is a method of manufacturing a liquid crystal element including a liquid crystal alignment film, and the liquid crystal alignment film is formed using the liquid crystal alignment agent of [1].

[3] A liquid crystal alignment film formed using the liquid crystal alignment agent of [1].

[4] A liquid crystal element including the liquid crystal alignment film of [3].

According to the present invention, it is possible to prepare a liquid crystal alignment agent that has good coating properties on a substrate and is less likely to cause deterioration of an inkjet head. In addition, liquid crystal cells with excellent afterimage characteristics can be produced. pieces.

<<Liquid crystal alignment agent>>

The liquid crystal alignment agent of the present disclosure contains a polymer component and a solvent component. Each component contained in the liquid crystal alignment agent and other components optionally blended as necessary will be described below.

<<Polymer composition>>

Examples of the polymer component contained in the liquid crystal alignment agent include polyamide acid, polyamide ester, polyamide imide, polyorganosiloxane, polyester, polyamide, and polyamide imide. , polybenzoxazole precursor, polybenzoxazole, cellulose derivatives, polyacetal, polymers having structural units derived from monomers having polymerizable unsaturated bonds (hereinafter also referred to as "polymerization" (Q)"), etc. are polymers with the main skeleton. From the viewpoint of fully ensuring the performance of the liquid crystal element, the polymer component is preferably selected from the group consisting of polyamide acid, polyamide ester, polyimide, polyorganosiloxane, polyamide and polymer ( At least one of the groups composed of Q).

<Polyamide>

Polyamic acid can be obtained by reacting tetracarboxylic dianhydride and a diamine compound.

(tetracarboxylic dianhydride)

Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and the like. Specific examples of these include, for example, aliphatic tetracarboxylic dianhydride: 1,2,3,4-butanetetracarboxylic dianhydride, etc.; examples of alicyclic tetracarboxylic dianhydride include: 1,2 ,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic 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-spirocyclo-3'-(tetrahydrofuran-2',5'-dione), 2,4,6,8-tetracarboxy Bicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetracycline Ketones, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; examples of aromatic tetracarboxylic dianhydrides include: pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene Ethylene glycol bis-trimellitic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carbonyl diphthalic anhydride , 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2'-dichloro-3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2 , 2'-dimethyl-3,3',4,4'-diphenyltetracarboxylic dianhydride, etc. In addition, the tetracarboxylic acid described in Japanese Patent Laid-Open No. 2010-97188 can also be used. Acid dianhydride. 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 in the synthesis of polyamide include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these diamines include aliphatic diamines such as m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Amine, etc.; examples of alicyclic diamines include: 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc.; examples of aromatic diamines include: dodecane Oxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2, 4-Diaminobenzene, Pentadecyloxy-2,5-diaminobenzene, Octadecyloxy-2,5-diaminobenzene, Cholestanyloxy-3,5-diaminobenzene Benzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5 -Cholestanyl diaminobenzoate, 3,5-cholesteryl diaminobenzoate, 3,5-lanosteryl alkyl 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)benzene base)-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 independently single bonds, -O-, *-COO- or *-OCO- (where "*" represents the bond with ^I is an alkanediyl group with 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group with 1 to 3 carbon atoms, a is 0 or 1, b is an integer from 0 to 2, and c is an integer from 1 to 20. d is 0 or 1. Among them, a and b will not become 0 at the same time)

Represented compounds, diamines having a cinnamic acid structure in the side chain, and other side chain diamines: p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Thioether, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-amine phenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-amine phenoxy)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-amine phenyl)hexane, 1,4-bis(4-aminophenylsulfonyl)butane, bis[2-(4-aminophenyl)ethyl]adipic acid, N,N-bis (4-Aminophenyl)methylamine, 2,6-diaminopyridine, 1,4-bis(4-aminophenyl)-piperazine, N,N'-bis(4-aminobenzene) methyl)-benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 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)]diphenylamine, 4,4'-diaminobenzoaniline , 4,4'-diaminostilbene, 4,4'-diaminodiphenylamine, 1,3-bis(4-aminophenylethyl)urea, 1,3-bis(4- Aminobenzyl)urea, 1,4-bis(4-aminophenyl)-piperazine, N-(4-aminophenylethyl)-N-methylamine, N,N'-bis( Main chain diamines such as 4-aminophenyl)-N,N'-dimethylbenzidine; examples of diaminoorganosiloxane include 1,3-bis(3-aminopropyl)- In addition to tetramethyldisiloxane, the diamine described in Japanese Patent Application Laid-Open No. 2010-97188 can also be used.

(Synthesis of polyamide)

Polyamic acid can be obtained by reacting the above-described tetracarboxylic dianhydride and a diamine compound together with a molecular weight adjuster if necessary. The usage ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amine group of the diamine compound. Equivalent ratio. Examples of the molecular weight adjuster include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate, isocyanate Naphthyl acid naphthyl ester and other monoisocyanate compounds, etc. The usage ratio of the molecular weight regulator is preferably 20 parts by mass or less based on 100 parts by mass in total of the tetracarboxylic dianhydride and the diamine compound used.

The synthesis reaction of polyamide is preferably carried out in an organic solvent. At this time, the reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Particularly good organic solvents are preferably selected from the group consisting of N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyltrisoxide, One or more of the group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphonotriamine, m-cresol, xylenol and halogenated phenol is used as a solvent, or one or more of these is used with Mixtures of other organic solvents (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.). The usage amount (a) of the organic solvent is preferably set so that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 mass % to 50 mass % with respect to the total amount of the reaction solution (a + b). quantity. Dissolve the polyamide The resulting reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the polyamide contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

<Polyamide>

Polyamic acid ester can be obtained, for example, by the following method: [I] A method of reacting the polyamic acid obtained by the above-described synthesis reaction with an esterifying agent; [II] A method of reacting a tetracarboxylic acid diester with A method of reacting a diamine compound; [III] A method of reacting a tetracarboxylic acid diester dihalide with a diamine compound, etc. The polyamic acid ester contained in the liquid crystal alignment agent may only have a amino acid ester structure, or may be a partial esterification product in which the amino acid structure and the amino acid ester structure coexist. Furthermore, the reaction solution obtained by dissolving the polyamic acid ester can be directly used for the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

<Polyimide>

Polyamide imide can be obtained, for example, by dehydrating, ring-closing, and imidizing the polyamide acid synthesized as described above. The polyamide imide may be a complete amide imide obtained by dehydrating and ring-closing all the amide acid structures of the polyamide acid as its precursor, or may be a dehydration and ring-closing product of only a part of the amide acid structure. It is a partial amide imide compound in which the amide acid structure and the amide imine ring structure coexist. The polyimide preferably has an imidization rate of 20% to 99%, more preferably 30% to 90%. The acyl imidization rate represents the ratio of the number of amide imine ring structures to the total number of amide acid structures and the number of amide imine ring structures of the polyamide imide as a percentage. Here, part of the imine ring may be an isoimine ring.

The dehydration ring closure of polyamide is preferably carried out by the following method: adding polyamide Amino acid is dissolved in an organic solvent, a dehydrating agent and a dehydration closed-loop catalyst are added to the solution and heated if necessary. In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The usage amount of the dehydrating agent is preferably 0.01 mole to 20 mole with respect to 1 mole of the amide acid structure of the polyamide acid. As the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, methylpyridine, dipyridine, and triethylamine can be used. The usage amount of the dehydration closed-loop catalyst is preferably 0.01 mole to 10 mole relative to 1 mole of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include those exemplified as those used in the synthesis of polyamide. The reaction temperature of the dehydration loop-closure reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hours to 120 hours. The reaction solution containing polyimide can be directly used for the preparation of the liquid crystal alignment agent, or the polyimide can be separated and used for the preparation of the liquid crystal alignment agent. Polyimide can also be obtained by imidization of polyamide ester.

<Polyorganosiloxane>

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, and 3-glycidoxysilane. Propyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(methyl ) Acryloxypropyltrimethoxysilane, trimethoxysilylpropylsuccinic anhydride, etc. A hydrolyzable silane compound may be used individually by 1 type, and may be used in combination of 2 or more types. "(Meth)acryloxy" means "acryloxy" and "methacryloxy".

The hydrolysis and condensation reactions are performed by reacting one or more silane compounds with water, preferably in the presence of an appropriate catalyst and organic solvent. During the reaction, the usage ratio of water is 1 mole relative to the silane compound (total amount), preferably 1 mole to 30 mole. Examples of the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. The usage amount of the catalyst varies depending on the type of catalyst, reaction conditions such as temperature, etc., but is, for example, 0.01 times molar to 3 times molar relative to the total amount of silane compounds. Examples of the organic solvent used include hydrocarbons, ketones, esters, ethers, alcohols, and the like. It is preferred to use a water-insoluble or poorly water-soluble organic solvent. The usage ratio of the organic solvent is preferably 10 to 10,000 parts by mass relative to 100 parts by mass in total of the silane compounds used in the reaction. The reaction is preferably carried out by heating in an oil bath or the like. The heating temperature at this time is preferably 130°C or lower, and the heating time is preferably 0.5 to 12 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is dried with a desiccant if necessary, and then the solvent is removed, thereby obtaining the target polyorganosiloxane. Furthermore, the synthesis method of polyorganosiloxane is not limited to the above-mentioned hydrolysis and condensation reactions. For example, it can also be carried out by reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

In the case where the liquid crystal alignment agent contains a polyorganosiloxane having a functional group such as a photoalignment group or a pretilt angle imparting group in the side chain, for example, by using an epoxy group-containing material in at least part of the raw material The target can be obtained by polymerizing a silane compound to synthesize a polyorganosiloxane having an epoxy group in the side chain, and then reacting the epoxy group-containing polyorganosiloxane with a carboxylic acid having a functional functional group Polyorganosiloxane. Alternatively, hydrolyzable silylation materials having functional functional groups can also be used. The compound is used in the polymerization of monomers.

<Polyamide>

Polyamide can be obtained by a method of reacting a dicarboxylic acid and a diamine compound. The dicarboxylic acid is preferably chlorinated using an appropriate chlorinating agent such as thionite chloride and then used for reaction with the diamine compound.

The dicarboxylic acid used in the synthesis of polyamide is not particularly limited. Examples include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, and 2-methylhexane. Aliphatic dicarboxylic acids such as diacids and fumaric acid; alicyclic dicarboxylic acids such as cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, and cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid Dicarboxylic acid, terephthalic acid, 5-methylisophthalic acid, 2,5-dimethylterephthalic acid, 4-carboxycinnamic acid, 3,3'-[4,4'-(methylene Aromatic dicarboxylic acids such as di-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dibutyric acid; etc. Examples of the diamine compound used in the synthesis include the diamine compounds exemplified in the description of the polyamide. A dicarboxylic acid and a diamine compound may be used individually by 1 type each, and may be used in combination of 2 or more types.

The reaction between the dicarboxylic acid and the diamine compound is preferably carried out in the presence of a base in an organic solvent. At this time, the usage 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 amine group of the diamine compound. The reaction temperature is preferably 0°C to 200°C, and the reaction time is preferably 0.5 hours to 48 hours. As the organic solvent, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsairnoxide, N-methyl-2-pyrrolidone, etc. can be preferably used. As the base, pyridine, triethylamine, N-ethylamine can be preferably used. -N,N-diisopropylamine and other tertiary amines. The usage ratio of the base is preferably 2 moles to 4 moles relative to 1 mole of the diamine compound. The solution obtained by the reaction can be directly used for the preparation of the liquid crystal alignment agent, or the polyamide contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

<Polymer(Q)>

Examples of the monomer having a polymerizable unsaturated bond include compounds having a (meth)acryl group, a vinyl group, a styrene 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 vinyl benzoic acid: (meth)acrylic acid alkyl ester, Cycloalkyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, (meth)acrylic acid 2-Hydroxyethyl ester, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4-hydroxyacrylate Unsaturated carboxylic acid esters such as butyl glycidyl ether: unsaturated polycarboxylic acid anhydrides such as maleic anhydride: (meth)acrylic compounds such as styrene, methylstyrene, divinylbenzene and other aromatic vinyl compounds; Conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene; N-methylmaleimide, N-cyclohexylmaleimide, N-benzene Maleimide-based compounds and other compounds containing maleimide groups; etc. 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 this specification, "(meth)acrylic group" means including "acrylic group" and "methacrylic group".

The polymer (Q) can be obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. As the polymerization initiator used, for example Preferred are 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy -2,4-Dimethylvaleronitrile) and other azo compounds. The usage ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used in the reaction. The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, etc. Preferably they are diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, etc. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 hour to 36 hours. The usage amount (a) of the organic solvent is preferably an amount such that the total amount (b) of the monomers used in the reaction becomes 0.1 mass % to 60 mass % with respect to the total amount of the reaction solution (a + b). . The polymer solution obtained by the reaction can be directly used for the preparation of the liquid crystal alignment agent, or the polymer (Q) contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

The solution viscosity of the polymer used in the preparation of the liquid crystal alignment agent is preferably 10 mPa when prepared and measured under the conditions described below. s~800mPa. s, preferably 15mPa. s~500mPa. s. Furthermore, the solution viscosity (mPa.s) is a good solvent for the polymer used (in the case of polyamic acid, polyamic acid ester and polyimide, it is γ-butyrolactone, N- A polymer solution with a concentration of 10% by mass prepared from methyl-2-pyrrolidone, etc., measured 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 polymer, and is preferably 1,000 to 500,000, more preferably It is 2,000~300,000. Conversion from Mw to polystyrene measured by GPC The molecular weight distribution (Mw/Mn) represented by the ratio of the number average molecular weight (Mn) is preferably 7 or less, more preferably 5 or less. The polymer used in the preparation of the liquid crystal alignment agent may be one type, or two or more types may be combined.

From the viewpoint of liquid crystal alignment, affinity with liquid crystal, and mechanical strength, the polymer component contained in the liquid crystal alignment agent is preferably one selected from the group consisting of polyamide acid, polyamide ester, At least one of the group consisting of polyimide and polyorganosiloxane. In addition, the polymer component particularly preferably contains at least one selected from the group consisting of polyamide acid, polyamide imide, and polyamide ester as a main component. Here, the main component refers to the component with the largest content on a mass basis, for example, a component with a content of 50% by mass or more. That is, among the polymer components, at least one selected from the group consisting of polyamide acid, polyamide imide, and polyamide ester is preferably 50 mass % or more relative to the total amount of the polymer components. , more preferably 60 mass% or more, further preferably 80 mass% or more.

<<Compound[A]>>

The liquid crystal alignment agent of the present disclosure contains compound [A] represented by the following formula (1).

(R ² )x-Ar ¹ -R ¹ ...(1)

(In formula (1), Ar ¹ is an aromatic ring group with a valence of (x+1), and R ² is an alkyl group with 1 to 3 carbon atoms, a hydroxyalkyl group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms. Oxygen group, x is 0 or 1. R ¹ is a hydroxyalkyl group with 1 to 3 carbon atoms or an alkoxy group with 1 to 3 carbon atoms)

By containing compound [A], the following liquid crystal alignment agent can be obtained: the polymer components are uniform It is uniformly dissolved in solvent components, has good wettability and spreadability when applied to a substrate, and is unlikely to cause deterioration of the inkjet head.

In the 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 heterocyclic ring. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, anthracene rings, etc.; aromatic heterocyclic rings include nitrogen-containing heterocycles such as pyrrole rings, pyridine rings, pyrimidine rings, and pyridazine rings, and furan rings. Oxygen-containing heterocycles such as ring and oxazole ring, sulfur-containing heterocycles such as thiol ring and thiazole ring, etc. Furthermore, among the above, the oxazole ring and the thiazole ring are also nitrogen-containing heterocycles. As Ar ¹ , among these, a group obtained by removing (x+1) hydrogen atoms from the ring portion of a benzene ring or a heterofive-membered hetero ring is preferred, and a group obtained by removing (x+1) hydrogen atoms from the ring portion of a benzene ring or a furan ring is particularly preferred. A group after x+1) hydrogen atoms.

Regarding R ¹ in the formula (1), examples of the hydroxyalkyl group having 1 to 3 carbon atoms include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, and 2-hydroxy Propyl, 3-hydroxypropyl. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group, propoxy group, and 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. Regarding specific examples when R ² is a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, the above explanation for R ¹ can be applied. R ² is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

x is preferably 0.

Among the above, compound [A] is particularly preferably selected from 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) At least one member of the group of compounds represented.

(In formula (1-1) to formula (1-3), n and r are each independently an integer from 1 to 3, and m is an integer from 0 to 2. R ³ is an alkyl group with 1 to 3 carbon atoms, and carbon Hydroxyalkyl group with 1 to 3 carbon atoms or alkoxy group with 1 to 3 carbon atoms, y is 0 or 1)

In the formulas (1-1) to (1-3), regarding R ³ , the description of specific examples and preferred examples of R ² can be applied. The bonding position of R ³ is not particularly limited, but is preferably ortho position with respect to the group “-(CH ₂ ) _n -OH” and the group “-O-(CH ₂ ) _m -CH ₃ ”.

y is preferably 0.

As preferred specific examples of compound [A], the compound represented by the formula (1-1) includes compounds represented by the following formulas (1-1-1) to formula (1-1-3) respectively. ; The compound represented by the formula (1-2) can include compounds represented by the following formula (1-2-1) ~ formula (1-2-4) respectively; as the formula (1-3) Examples of the compounds represented include compounds represented by the following formulas (1-3-1) to formula (1-3-6).

[Chemical 3]

As the compound [A], among the compounds represented by the formulas (1-1) to (1-3) respectively, a compound in which y=0 is preferred. Among these, the compounds represented by the above formulas (1-1-1) and formula (1-2-1) are preferred in terms of having more excellent inkjet coating properties, and it is more difficult to use the inkjet coating properties. In terms of deterioration of the ink head, compounds represented by the formulas (1-1-1) and (1-3-1) are preferred. In addition, as the compound [A], one type may be used alone, or two or more types may be used in combination.

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

Furthermore, compound [A] can improve the solubility of the polymer component of the liquid crystal alignment agent, and therefore can serve as a good solvent for N-methyl-2-pyrrolidone (N-methyl- 2-pyrrolidone (NMP) is used as an alternative solvent. In this case, the content ratio of NMP in the liquid crystal alignment agent is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 1 mass% or less relative to the total amount of solvent components of the liquid crystal alignment agent.

<<Other ingredients>>

If necessary, the liquid crystal alignment agent may further contain components different from the polymer component and compound [A] (hereinafter also referred to as "other components").

<Solvent[B]>

For the purpose of improving the wettability and spreadability of the liquid crystal alignment agent, the liquid crystal alignment agent may further include, in addition to the polymer component and compound [A], a solvent selected from the group consisting of ether solvents and alcohol solvents within the scope that does not impair the effects of the present disclosure. At least one solvent (hereinafter, also referred to as "solvent [B]") from the group consisting of a solvent, a linear ester solvent, and a ketone solvent.

Specific examples of the solvent [B] include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, and ethylene glycol monopropyl ether. Butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol methyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether ethyl acid ester (propylene glycol methyl ether acetate, PGMEA), 3-methoxy-1-butanol, tetrahydrofuran, diisoamyl ether, etc.; examples of alcohol solvents include: methanol, ethanol, isopropyl alcohol, cyclohexanol, Ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, 3-methoxy-3-methylbutanol, benzyl alcohol, etc.; examples of chain ester solvents include: lactic acid Ethyl ester, butyl lactate, Methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isobutyric acid Pentyl ester, etc.; ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopentanone, 3-methylcyclohexanone, 4-methyl Cyclohexanone, diisobutyl ketone, etc.

The solvent [B] is preferably at least one selected from the group consisting of an ether solvent, an alcohol solvent, and a ketone solvent, in terms of further enhancing the coating property improving effect. One type, more preferably at least one type selected from the group consisting of ether solvents having 8 or less carbon atoms, alcohol solvents, and cyclic ketone solvents. Specifically, the solvent [B] is particularly preferably selected from the group consisting of ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, and diacetone alcohol. Composed of ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol and cyclopentanone one of the groups. In addition, as the solvent [B], one type can be used alone or two or more types can be used in combination.

For the purpose of further improving the solubility of the polymer component or the wetting and spreading properties of the liquid crystal alignment agent, the liquid crystal alignment agent may further include a solvent different from the solvent [B] (hereinafter also referred to as "other solvents") as other Element. Examples of other solvents include aprotic polar solvents, halogenated hydrocarbon solvents, hydrocarbon solvents, and the like. Specific examples of other solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidine. Ketone, γ-butyrolactone, Propyl carbonate, 3-butoxy-N,N-dimethylpropylamide, 3-methoxy-N,N-dimethylpropylamide, 3-hexyloxy-N,N-di Methylpropylamide, isopropoxy-N-isopropyl-propylamide, n-butoxy-N-isopropyl-propylamide, etc.; examples of halogenated hydrocarbon solvents include: methylene chloride, 1 , 2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, etc.; examples of hydrocarbon solvents include: hexane, heptane, octane, benzene, toluene, xylene, etc. Among the above, other solvents are preferably aprotic polar solvents, and more preferably are selected from γ-butyrolactone, N-ethyl-2-pyrrolidone, propyl carbonate, and 1,3-dimethyl. At least one of the group consisting of base-2-imidazolidinones. In addition, as other solvents, one type may be used alone or two or more types may be used in combination.

From the viewpoint of improving the coatability of the liquid crystal alignment agent and appropriately suppressing the deterioration of the inkjet head, the content ratio of the compound [A] relative to the total amount of the solvent contained in the liquid crystal alignment agent is preferably set to More than 10% by mass. The content ratio is more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more relative to the total amount of the solvent. In addition, the content ratio of the compound [A] is preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 80 mass% or less relative to the total amount of the solvent contained in the liquid crystal alignment agent.

When the liquid crystal alignment agent contains solvent [B], the content ratio of solvent [B] relative to the total amount of solvents contained in the liquid crystal alignment agent is preferably 5 mass % or more, and more preferably 10 mass % or more. In addition, the content ratio of the solvent [B] relative to the total amount of solvents in the liquid crystal alignment agent is preferably 90 mass% or less, more preferably 85 mass% or less, and still more preferably 80 mass% or less.

The content ratio of other solvents relative to the total amount of solvents contained in the liquid crystal alignment agent The amount is preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 60 mass% or less, and particularly preferably 50 mass% or less.

As other components that can be contained in the liquid crystal alignment agent, in addition to the above, examples include: epoxy group-containing compounds (such as N,N,N',N'-tetraglycidyl-m-xylylenediamine, N ,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.), functional silane compounds (such as 3-aminopropyltriethoxysilane, N-( 2-Aminoethyl)-3-aminopropylmethyldimethoxysilane, etc.), antioxidants, metal chelating compounds, hardening catalysts, hardening accelerators, surfactants, fillers, dispersants, Various additives such as photosensitizers. The blending ratio of these additives can be appropriately selected for each compound within a range that does not impair the effects of the present disclosure.

Among the components in the liquid crystal alignment agent, the proportion D of the total mass of the compound [A] and the solvent to the total mass of the liquid crystal alignment agent can be appropriately selected considering viscosity, volatility, etc., and is preferably 1% by mass~ 10 mass% range. When the ratio D is less than 1% by mass, the film thickness of the coating film becomes too small and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the ratio D exceeds 10 mass %, the film thickness of the coating film becomes too large and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coating properties tend to decrease. .

Furthermore, there is a reason why by using compound [A], it is possible to obtain the effect of suppressing the deterioration of the inkjet head while maintaining the coating properties of the liquid crystal alignment agent to the substrate well while maintaining the afterimage characteristics of the liquid crystal element well. It is not certain, but as one reason, it is thought to be caused by the chemical structure of compound [A]. Specifically, it can be speculated that when the liquid crystal alignment agent is coated on the substrate, due to the chemical structure of compound [A] (Structure represented by the above formula (1)) The alignment of the liquid crystal is controlled to a certain extent, thereby exhibiting good afterimage characteristics. However, this speculation does not limit the present invention.

<<Liquid crystal alignment film and liquid crystal elements>>

The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. Liquid crystal elements can be effectively used in various applications, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), digital Various display devices such as cameras, mobile phones, smartphones, various monitors, LCD TVs, and information displays, or dimming films, phase difference films, etc. When used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited. For example, it can be applied to a twisted nematic (TN) type, a super twisted nematic (Super Twisted Nematic, STN) type, and a vertical alignment type. (Including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), coplanar switching In various operation modes such as (In-Plane Switching, IPS) type, Fringe Field Switching (FFS) type, Optically Compensated Bend (OCB) type, etc.

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

(Step 1: Formation of coating film)

First, the liquid crystal alignment agent is coated on the substrate, and the coating surface is preferably heated to form a coating film on the substrate. As the substrate, for example, a transparent substrate containing the following materials can be used: glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether ester, polycarbonate, poly( Alicyclic olefins) and other plastics. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG Corporation, USA) containing tin oxide (SnO ₂ ), a film containing indium oxide-tin oxide (In ₂ O ₃ -SnO) can be used. ₂ ) Indium Tin Oxide (ITO) film, etc. When manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with patterned transparent conductive films are used. On the other hand, when manufacturing an IPS type or FFS type liquid crystal element, a substrate provided with electrodes including a transparent conductive film or metal film patterned into a comb-tooth shape and a counter substrate provided with no electrodes are used. As the metal film, for example, a film containing metal such as chromium can be used.

Coating the liquid crystal alignment agent on the substrate on the electrode formation surface is preferably carried out by offset printing, spin coating, roll coater, flexographic printing or inkjet printing. In particular, the liquid crystal alignment agent has good wettability and spreadability and can suppress deterioration of the resin member constituting the inkjet head. It can exhibit excellent printability when using the inkjet printing method and can suppress product defects. It is preferable in that it can reduce the rate and obtain a liquid crystal alignment film with high performance.

After applying the liquid crystal alignment agent, it is preferable to perform preheating (prebaking) for the purpose of preventing dripping of the applied liquid crystal alignment agent. The preferred pre-baking temperature is 30°C ~ 200°C, and the preferred pre-baking time is 0.25 minutes ~ 10 minutes. Then, for the sake of The solvent is completely removed, and a calcination (post-baking) step is performed for the purpose of thermally imidizing the amide structure of the polymer if necessary. The calcination temperature (post-baking temperature) is preferably 80°C to 300°C, and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm. After the liquid crystal alignment agent is coated on the substrate, the organic solvent is removed, thereby forming a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film.

(Step 2: Alignment processing)

When manufacturing a TN type, STN type, IPS type or FFS type liquid crystal display element, a process (alignment process) for imparting liquid crystal alignment capability to the coating film formed in step 1 is performed. Thereby, the alignment ability of liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. Examples of the alignment treatment include a rubbing treatment in which the coating film is rubbed in a certain direction using a roll wrapped with a cloth containing fibers such as nylon, rayon, and cotton; or a rubbing treatment using liquid crystal. The coating film formed on the substrate by the alignment agent is irradiated with light to impart liquid crystal alignment ability to the coating film, such as a photo-alignment process. On the other hand, when manufacturing a vertical alignment type liquid crystal element, the coating film formed in step 1 can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to alignment treatment (rubbing treatment, photo-alignment processing, etc.). The liquid crystal alignment agent suitable for vertical alignment type liquid crystal display elements can also be suitably used for polymer stable alignment (Polymer sustained alignment, PSA) type liquid crystal display elements.

(Step 3: Construction of LCD Cell)

A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed in the above manner, and arranging liquid crystal between the two facing substrates. Manufacturing LCD units Examples of the method include: (1) Arrange two substrates facing each other through a gap (spacer) so that the liquid crystal alignment films face each other, bond the peripheral portions of the two substrates using a sealant, and inject liquid crystal The method of filling the cell gap divided by the substrate surface and the sealant, and then sealing the injection hole, (2) applying the sealant to a predetermined position on one of the substrates on which the liquid crystal alignment film is formed, and then applying the sealant to the liquid crystal A method in which liquid crystal is dropped onto a predetermined number of locations on the alignment film surface, then attached to another substrate so that the liquid crystal alignment films face each other, and the liquid crystal is pressed and spread to the entire surface of the substrate (one drop filling (ODF) ) method) etc. Ideally, the produced liquid crystal cell is further heated until the liquid crystal used becomes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment during filling of the liquid crystal.

As the sealant, for example, epoxy resin containing a hardener and alumina balls as spacers can be used. As spacers, photo spacers, beads spacers, etc. can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferred. In addition, for example, cholesteric liquid crystal (cholesteric liquid crystal), chiral reagent, ferroelectric liquid crystal (ferroelectric liquid crystal), etc. can also be added to nematic liquid crystal or smectic liquid crystal. When manufacturing a PSA type liquid crystal display element, liquid crystal and a polymerizable monomer are arranged together between a pair of substrates, and after constructing a liquid crystal cell, light is irradiated with a voltage applied between a pair of electrodes. processing.

Next, attach a polarizing plate to the outer surface of the liquid crystal cell if necessary. Examples of polarizing plates include those in which a polarizing film called an "H film" in which polyvinyl alcohol is stretched and oriented on one side and absorbs iodine is sandwiched between cellulose acetate protective films. Polarizing plate, or polarizing plate including H film itself. In this way, a liquid crystal display element is obtained.

[Example]

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

In the following examples, the weight average molecular weight Mw of the polymer, the imidization rate of the 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 raw material compounds and polymers used in the following examples are ensured by repeating the synthesis at the synthesis scale shown in the following synthesis examples as necessary.

[Polymer weight average molecular weight Mw]

The weight average molecular weight Mw is a polystyrene-converted value measured by GPC under the following conditions.

Column: TSKgelGRCXLII manufactured by Tosoh Corporation

Solvent: Tetrahydrofuran, or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid

Temperature: 40℃

Pressure: 68kgf/ ^cm2

[Imination rate of polyimide]

Pour the solution of polyimide into pure water, dry the obtained precipitate under reduced pressure at room temperature, dissolve it in deuterated dimethylsulfoxide, use tetramethylsilane as the reference material, and dry it at room temperature. ¹ H-Nuclear Magnetic Resonance (NMR) was measured under . From the obtained ¹ H-NMR spectrum, the acyl imidization rate [%] was determined by the following mathematical formula (1).

Imination rate [%]=(1-(A ¹ /(A ² ×α)))×100…(1)

(In formula (1), A ¹ is the peak area of the proton derived from the NH group that appears near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamide The ratio of the number of other protons in the acid) relative to one proton of the NH group)

[Solution viscosity of polymer solution]

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

[Epoxy equivalent]

The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105.

The abbreviations of the compounds are as follows. In addition, the compound represented by formula (X) may be simply expressed as "compound (X)" below.

． Tetracarboxylic dianhydride and diamine compounds

[Chemical 4]

． Compound[A]

[Chemical 6]

<Synthesis of polymers>

[Synthesis Example 1: Synthesis of polyimide (PI-1)]

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride (TCA) as tetracarboxylic dianhydride and 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine ), and 10.5g (0.02 mol) of cholestyl 3,5-diaminobenzoate were dissolved in 166g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60°C for 6 hours , to obtain a solution containing 20% by mass of polyamide. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 90 mPa. s.

Next, NMP was added to the obtained polyamic acid solution to prepare a solution with a polyamic acid concentration of 7% by mass, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110° C. for 4 hours. . After the dehydration ring-closure reaction, use new NMP to replace the solvent in the system (through this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed from the system. The same is true below), thereby obtaining a solution containing chelate A 26% by mass solution of polyimide (PI-1) with an amination rate of approximately 68%. A small amount of the obtained polyimide solution was collected, and NMP was added to prepare a solution with a polyimide concentration of 10% by mass. The measured viscosity of the solution was 45 mPa. s. Then, the reaction The solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyimide (PI-1).

[Synthesis Example 2: Synthesis of polyimide (PI-2)]

110 g (0.50 mol) of TCA as tetracarboxylic dianhydride and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo- 3-furyl)naphtho[1,2-c]furan-1,3-dione 160g (0.50mol), PDA as diamine 91g (0.85mol), 1,3-bis(3-amine) propyl)tetramethyldisiloxane 25g (0.10 mol), and 3,6-bis(4-aminobenzyloxy)cholestane 25g (0.040 mol), and as monoamine 1.4 g (0.015 mol) of aniline was dissolved in 960 g of NMP, and the reaction was carried out at 60° C. for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution 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 a dehydration ring-closure reaction was performed at 110° C. for 4 hours. After the dehydration and ring-closure reaction, new γ-butyrolactone (GBL) is used to replace the solvent in the system, thereby obtaining polyimide (PI-2) 15 with an imidization rate of approximately 95%. The mass % solution is about 2,500g. A small amount of this solution was taken, and NMP was added to prepare a solution with a polyimide concentration of 10% by mass. The measured viscosity of the solution was 70 mPa. s. Then, the reaction solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyimide (PI-2).

[Synthesis Example 3: Synthesis of polyimide (PI-3)]

Except that the diamine used was changed to 0.08 mol of 3,5-diaminobenzoic acid and 0.02 mol of cholestanyloxy-2,4-diaminobenzene, the same method as in the above synthesis example was used. 1. Obtain the polyamide solution using the same method. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 80 mPa. s. Subsequently, imidization was performed in the same manner as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-3) with an imidization rate of approximately 65%. A small amount of the obtained polyimide solution was collected, and NMP was added to prepare a solution with a polyimide concentration of 10% by mass. The measured viscosity of the solution was 40 mPa. s. Then, the reaction solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyimide (PI-3).

[Synthesis Example 4: Synthesis of polyimide (PI-4)]

The tetracarboxylic dianhydride used was changed to 0.04 mol of 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride and pyromellitic acid dianhydride. The method was the same as in Synthesis Example 1 except that 0.02 mol of anhydride was used and the diamine used was changed to 0.06 mol of compound (DA-2) and 0.04 mol of compound (DA-1). A polyamide solution is obtained. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 75 mPa. s. Subsequently, imidization was performed in the same manner as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-4) with an imidization rate of approximately 50%. Dispense a small amount of the obtained polyimide solution and add NMP to prepare the polyimide concentration. It is a 10 mass% solution, and the measured viscosity of the solution is 40mPa. s. Then, the reaction solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining 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-cyclobutane tetracarboxylic dianhydride and 0.02 mol of pyromellitic dianhydride, and the diamine used was changed to In addition to 0.098 mol of 4-aminophenyl-4-aminobenzoate (compound (DA-3)) and 0.002 mol of compound (DA-4), the synthesis method was carried out with the above-mentioned Synthesis Example 1 The polyamide solution was obtained in the same way. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 80 mPa. s. Subsequently, imidization was performed in the same manner as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-5) with an imidization rate of approximately 65%. A small amount of the obtained polyimide solution was collected, and NMP was added to prepare a solution with a polyimide concentration of 10% by mass. The measured viscosity of the solution was 50 mPa. s. Then, the reaction solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyimide (PI-5).

[Synthesis Example 6: Synthesis of polyamic acid (PA-1)]

200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) as tetracarboxylic dianhydride and 2,2'-dimethyl-4,4 as diamine '-Diaminobiphenyl 210g (1.0 mol) dissolved in a mixed solvent of 370g NMP and 3,300g gamma-butyrolactone (GBL) , the reaction was carried out for 3 hours at 40°C, and the solid content concentration was 10 mass% and the solution viscosity was 160mPa. s polyamide solution. Then, the polyamic acid solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyamide (PA-1).

[Synthesis Example 7: Synthesis of polyamic acid (PA-2)]

7.0 g of TCA (0.031 mol) as tetracarboxylic dianhydride and 13 g of compound (DA-5) as a diamine (equivalent to 1 mol relative to 1 mol of TCA) were dissolved in 80 g of NMP, and the mixture was dissolved in 60 The reaction was performed at ℃ for 4 hours, thereby obtaining a solution containing 20% by mass of polyamide (PA-2). The solution viscosity of the polyamide solution is 2,000mPa. s. In addition, compound (DA-5) was synthesized according to the description of Japanese Patent Application Laid-Open No. 2011-100099. Then, the polyamic acid solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyamide (PA-2).

[Synthesis Example 8: Synthesis of polyamic acid (PA-3)]

In addition to changing the diamine used to 0.7 mol of 1,3-bis(4-aminophenylethyl)urea (compound (DA-6)) and 0.3 mol of compound (DA-7), A polyamide solution was obtained in the same manner as in Synthesis Example 6. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 100 mPa. s. Then, the polyamic acid solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40°C for 15 hours under reduced pressure to obtain polyester. Amino acid (PA-3).

[Synthesis Example 9: Synthesis of polyamic acid (PA-4)]

The tetracarboxylic dianhydride used was changed to 1.0 mol of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, and the diamine used was changed to p-phenylene The method was the same as in Synthesis Example 6 except that 0.3 mol of diamine, 0.2 mol of compound (DA-7), and 0.5 mol of 1,2-bis(4-aminophenoxy)ethane were used. The polyamide acid solution was obtained by the method. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 90 mPa. s. Then, the polyamic acid solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyamide (PA-4).

[Synthesis Example 10: Synthesis of polyamide (PA-5)]

The diamine used was changed to 0.2 mol of 2,4-diamino-N,N-diallylaniline, 0.2 mol of 4,4'-diaminodiphenylamine, and 4,4' A polyamic acid solution was obtained in the same manner as in Synthesis Example 6 except that - 0.6 mol of diaminodiphenylmethane. A small amount of the obtained polyamic acid solution was collected, and NMP was added to prepare a solution with a polyamic acid concentration of 10% by mass. The measured viscosity of the solution was 95 mPa. s. Then, the polyamic acid solution was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining polyamide (PA-5).

[Synthesis Example 11: Synthesis of polyamide (PA-6)]

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

[Synthesis Example 12: Synthesis of polyamide ester (PAE-1)]

Add 0.035 mol of 2,4-bis(methoxycarbonyl)-1,3-dimethylcyclobutane-1,3-dicarboxylic acid to 20 ml of thionite chloride, and add a catalyst amount of N, N-dimethylformamide and then stirred at 80°C for 1 hour. Then, the reaction liquid was concentrated, and the residue was dissolved in 113 g of γ-butyrolactone (GBL) (this solution was referred to as reaction liquid A). Separately, 0.01 mole of p-phenylenediamine, 0.01 mole of 1,2-bis(4-aminophenoxy)ethane, and 0.014 mole of compound (DA-8) were added to 6.9g of pyridine, 44.5g of NMP, and Dissolve it in 33.5 g of GBL and cool it to 0°C. Then, the reaction solution A was slowly added dropwise to the solution over 1 hour, and after the dropwise addition was completed, the mixture was stirred at room temperature for 4 hours. The obtained polyamic acid ester solution was added dropwise to 800 ml of pure water while stirring, and the precipitated precipitate was filtered. Next, the mixture was washed five 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 polyamide ester (PAE-1) was 34,000.

[Synthesis Example 13: Synthesis of polyorganosiloxane (APS-1)]

Add 100.0g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500g of methyl isobutyl ketone and triethylamine to a reaction vessel equipped with a mixer, thermometer, dropping funnel and reflux cooling tube. 10.0g, mix at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was performed at 80° C. for 6 hours while stirring under reflux. After the reaction is completed, the organic layer is taken out and washed with 0.2 mass% ammonium nitrate aqueous solution until the washed water becomes neutral. The solvent and water are then distilled under reduced pressure to obtain the reaction in the form of a viscous transparent liquid. Polyorganosiloxane (EPS-1). The reactive polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis, and as a result, a peak based on the epoxy group was obtained near the chemical shift (δ) = 3.2 ppm, which was consistent with the theoretical intensity, confirming that No side reactions of epoxy groups occurred during the reaction. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g/mol.

Next, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, and 4-(dodecyloxy) as a reactive compound were added to a 200 mL three-necked flask. 3.98 g of benzoic acid and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were reacted at 100° C. for 48 hours with stirring. After the reaction, ethyl acetate was added to the reaction mixture, the obtained solution was washed three times, the organic layer was dried using magnesium sulfate, and the solvent was evaporated to obtain liquid crystal alignment polyorganosiloxane (APS-1 )9.0g. The weight average molecular weight Mw of the obtained polymer was 9,900.

<Preparation and Evaluation of Liquid Crystal Alignment Agent>

[Example 1]

1. Preparation of liquid crystal alignment agent

To the polyimide (PI-1) obtained in Synthesis Example 1, 3-phenylpropan-1-ol (compound a), γ-butyrolactone (γBL) and butyl cellosolve (BC) were added , to prepare a solution with a polymer concentration of 3.5% by mass and a solvent mixing ratio of compound a: γBL: BC = 40:30:30 (mass ratio). After the solution was sufficiently stirred, it was filtered using a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (S-1). Furthermore, the liquid crystal alignment agent (S-1) is mainly used to manufacture vertical alignment type liquid crystal display elements.

2. Evaluation of inkjet coating properties

As a substrate for coating the liquid crystal alignment agent, a glass substrate with a transparent electrode containing ITO was heated on a hot plate at 200°C for 1 minute, and then ultraviolet/ozone cleaning was performed so that the water contact angle of the transparent electrode surface was just 10 ° below the substrate. On the substrate, use an inkjet coater (manufactured by Shibaura Mechatronics Co., Ltd.) to apply the liquid crystal alignment agent (S-1) prepared in 1. to the glass substrate with a transparent electrode. on the transparent electrode surface. The coating conditions at this time were 2,500 times/(nozzle, minute) and a discharge amount of 250 mg/10 seconds for 2 round-trip coatings (4 times in total). After application, the substrate was left to stand for 1 minute, and then the substrate was heated at 50° C. to form a coating film with an average film thickness of 0.1 μm. The obtained coating film was observed with the naked eye under the irradiation of an interference fringe measurement lamp (sodium lamp), and unevenness and dents were evaluated.

In addition, the same operation as described above was performed except that the heating temperature during coating film formation was changed from 50°C to 60°C and 80°C, and the presence or absence of unevenness and dents in the coating film was observed. No unevenness or concavity was found at any heating temperature of 50℃, 60℃ and 80℃. The case where both unevenness and dents are found is regarded as "Good A (◎)" in inkjet coating properties, and the case where at least one of unevenness and dents is found at one of the heating temperatures of 50°C, 60°C, and 80°C is regarded as "Good A (◎)". For "Good B (○)", the case where at least one of unevenness and dents is found at two heating temperatures is set as "OK (△)", and when unevenness and dents are found at all heating temperatures, it is set as "OK (△)" If at least one of the above is determined as "Defect (×)". As a result, the evaluation was "Good B" in this example.

3. Evaluation of long-term stability of inkjet heads

The following method is used to evaluate the long-term stability of the inkjet head, thereby evaluating the impact of the liquid crystal alignment agent on the inkjet head. The evaluation used the KM1024i material compatibility kit manufactured by Konica Minolta. Furthermore, the so-called material compatibility kit is a sample piece used to test the solvent resistance of the components of the inkjet head. Here, a variety of cured resins in the sample pieces were used for the test.

First, after confirming the color and surface state of the sample piece, the mass of the sample piece (mass before immersion W1) is measured. Next, 100 ml of the solvent used in the preparation of the liquid crystal alignment agent (compound a: γBL: BC = 40: 30: 30 (mass ratio)) was weighed into a sealable glass bottle, and then the sample piece was immersed and stored at 50°C. 4 weeks. After 4 weeks, the sample piece was taken out of the glass bottle, and the solvent adhering to the surface of the sample piece was removed by air blowing, and then the color change, the presence of cracks, and the presence of dissolution were visually confirmed. Evaluation was based on changes compared to before immersion. Evaluation is performed as follows.

． Regarding color change: If there is no color change, set it as "Good (○)". If the color changes slightly, it is rated as "acceptable (△)", and if the color changes significantly, it is rated as "poor (×)".

． Regarding the presence or absence of cracks: The case where no cracks occurred was regarded as "good (○)", and the case where cracks occurred was regarded as "poor (×)".

． Regarding the presence or absence of dissolution: The case where resin dissolution was not confirmed by palpation was regarded as "good (○)", and the case where dissolution was observed was regarded as "poor (×)".

In addition, the mass of the sample piece after the sample piece was immersed in the solvent (mass after immersion W2) was measured, and the ratio α of the mass increased from the mass before immersion W1 was calculated by the following equation (2).

a[%]=((W2-W1)/W1)×100...(2)

Regarding evaluation, when the ratio α is less than 10%, it is regarded as "Good A (◎)", when it is more than 10% and less than 30%, it is regarded as "Good B (○)", when it is more than 30% and less than 50%, it is regarded as "Good B (○)" Set it as "Acceptable (△)" when it exceeds 50%, and set it as "Defect (×)" when it exceeds 50%. In addition, the lower the ratio α is, the more difficult it is for the solvent to be evaluated to swell the components of the inkjet head, and thus the better. 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 quality change was "acceptable".

4. Manufacturing of vertical alignment liquid crystal display elements

Use a spinner to apply the liquid crystal alignment agent (S-1) on a pair (2 pieces) of glass substrates with transparent electrodes containing ITO films, and preheat for 1 minute using a hot plate at 80°C. bake. Then, in an oven replaced with nitrogen, the film was heated (post-baked) at 200° C. for 1 hour to remove the solvent, thereby forming a coating film (liquid crystal alignment film) with a film thickness of 0.08 μm. This coating film was rubbed using a rubbing machine having a roller around which rayon cloth was wound, with a roller rotation speed of 400 rpm, a platform moving speed of 3 cm/second, and a gross intrusion length of 0.1 mm. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then dried in a clean oven at 100° C. for 10 minutes, thereby obtaining a substrate with a liquid crystal alignment film. This operation is repeated to obtain a pair (2 pieces) of substrates with liquid crystal alignment films. Furthermore, the rubbing treatment is a weak rubbing treatment for the purpose of controlling the collapse of the liquid crystal and performing alignment division in a simple manner.

An epoxy resin adhesive containing alumina balls with a diameter of 3.5 μm is applied to the outer periphery of the surface with a liquid crystal alignment film of one of the substrates by screen printing, and then the liquid crystals of the pair of substrates are aligned. The film surfaces faced each other, were overlapped and pressure-bonded, and heated at 150° C. for 1 hour to thermally harden the adhesive. Next, after filling the gap of the substrate with a negative liquid crystal (MLC-6608 manufactured by Merck) from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive, and further, in order to eliminate the flow during liquid crystal injection Alignment, heated at 150°C for 10 minutes and then slowly cooled to room temperature. Furthermore, the polarizing plates of the two polarizing plates are bonded to both outer surfaces of the substrate so that the polarizing directions of the two polarizing plates are orthogonal to each other, thereby manufacturing a liquid crystal display element.

5. Evaluation of deviation characteristics of pretilt angle (post-bake margin) relative to temperature unevenness of post-bake

According to the method of 4. above, the pretilt of the liquid crystal display elements obtained by making the liquid crystal alignment film at different post-baking temperatures (120°C, 180°C and 230°C) was measured. horn. The measured value at 230°C is used as the reference pretilt angle θp, and the pretilt angle relative to the temperature unevenness of the post-baking is evaluated based on the difference Δθ (=|θp-θa|) between the reference pretilt angle θp and the measured value θa deviation characteristics. Furthermore, it can be said that the smaller Δθ is, the smaller the deviation of the pretilt angle relative to the temperature unevenness is and the more excellent it is. The measurement of the pretilt angle will be based on the non-patent literature (T.J. Scheffer et.al.), Journal of Applied Physics (J.Appl.Phys.), Volume 19, Page 2013 (vo.19, p.2013 ) (1980)), the value of the inclination angle of the liquid crystal molecules relative to the substrate surface measured by the crystal rotation method using He-Ne laser light is set as the pretilt angle [°]. Regarding evaluation, the case where Δθ is 0.2° or less is regarded as "good (○)", the case where it is greater than 0.2° and less than 0.5° is regarded as "acceptable (△)", and the case where Δθ is 0.5° or more is regarded as "acceptable (△)" Defective (×)". As a result, in this Example, when the post-bake temperature was set to 180°C, the post-bake margin was evaluated as "good", and when it was set to 120°C, the post-bake margin was evaluated as "acceptable".

6. Evaluation of alternating current (AC) afterimage characteristics

In addition to the fact that the electrode structure is a two-system ITO electrode (electrode 1 and electrode 2) that can switch the application/non-application of voltage to the other, and that the polarizing plate is not bonded, the same as described in 4. A liquid crystal cell for evaluation was produced in the same method. The liquid crystal cell for evaluation was placed under conditions of 60° C., no voltage was applied to electrode 2, and an AC voltage of 10 V was applied to electrode 1 for 300 hours. Immediately after 300 hours, an AC voltage of 3 V was applied to both electrode 1 and electrode 2, and the difference in light transmittance ΔT [%] between the two electrodes was measured. At this time, the AC afterimage characteristics were evaluated as "good (○)" when ΔT was less than 2%, "acceptable (△)" when 2% or more and less than 3% were evaluated, and "good (△)" when ΔT was more than 3%. The condition evaluation is "Defect (×)". As a result, in this example, " "Good" evaluation.

7. Evaluation of direct current (DC) afterimage characteristics

Place the evaluation liquid crystal cell prepared in 6. above at 60°C, apply a DC voltage of 0.5 V to the electrode 1 for 24 hours, and determine the voltage remaining in the electrode 1 just after the DC voltage is cut off by the flicker elimination method. (residual DC voltage). At this time, the DC afterimage characteristics were evaluated as "good (○)" when the residual DC voltage was less than 100 mV, "acceptable (△)" when it was 100 mV or more and less than 300 mV, and "good (△)" when it was 300 mV or more. "Defect (×)". As a result, the evaluation was "good" in this example.

[Example 2 to Example 9 and Comparative Example 1 to Comparative Example 10]

A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the formula compositions were as described in Table 1 below. In addition, various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal alignment 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 formula composition was changed as described in Table 1 below. Furthermore, liquid crystal alignment agent (S-10) is mainly used to manufacture horizontal alignment type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agents

Except using the liquid crystal alignment agent (S-10), the inkjet coating properties and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1. These results are shown in Table 2 below.

3. Manufacturing of friction FFS type liquid crystal display elements

Use a spinner to apply the liquid crystal alignment agent (S-10) to a glass substrate on which a flat electrode (bottom electrode), an insulating layer and a comb-shaped electrode (top electrode) are laminated in sequence on one side, and on the opposite side where no electrode is provided. Each surface of the glass substrate was heated (pre-baked) using a hot plate at 80° C. for 1 minute. Then, drying (post-baking) was performed for 1 hour in a 200° C. oven that replaced nitrogen in the cavity to form a coating film with an average film thickness of 0.08 μm. Next, the surface of the coating film was rubbed using a rubbing machine having a roller wound with rayon cloth at a roller rotation speed of 500 rpm, a platform moving speed of 3 cm/second, and a gross intrusion length of 0.4 mm. Then, perform ultrasonic cleaning in ultrapure water for 1 minute, and then dry in a clean oven at 100° C. for 10 minutes, thereby obtaining a substrate with a liquid crystal alignment film.

Next, for a pair of substrates with a liquid crystal alignment film, a liquid crystal injection port was left at the edge of the surface on which the liquid crystal alignment film was formed, and an epoxy resin adhesive containing alumina balls with a diameter of 5.5 μm was screen printed and applied. . Then, the substrates were stacked and pressure-bonded, and the adhesive was thermally cured at 150° C. for 1 hour. Next, nematic liquid crystal (MLC-6221 manufactured by Merck) was filled from the liquid crystal injection port between the pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment when the liquid crystal is injected, the liquid crystal cell is manufactured by heating it at 120° C. and then slowly cooling it to room temperature. Furthermore, when a pair of substrates are overlapped, the rubbing directions of the respective substrates are made anti-parallel. In addition, the polarizing plates of the two polarizing plates were bonded together so that the polarizing directions of the two polarizing plates would be parallel to the rubbing direction and orthogonal to the rubbing direction, respectively. In addition, regarding the top electrode, the line width of the electrode was set to 4 μm, and the distance between the electrodes was set to 6 μm. In addition, the top electrode is driven by a four-system system using electrode A, electrode B, electrode C, and electrode D. electrode. In this case, the bottom electrode functions as a common electrode for all four systems of drive electrodes, and the areas of the four systems of drive electrodes each become a pixel area.

4. Evaluation of friction FFS type liquid crystal display elements

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1, except that the rubbed FFS type liquid crystal display element or liquid crystal cell produced according to the method of 3. was used. These results are shown in Table 2 below.

[Example 11, Example 12]

The liquid crystal alignment agent (S-11) and the liquid crystal alignment agent (S-12) were prepared in the same manner as in Example 1 except that the formula composition was changed as described in Table 1 below. In addition, the inkjet coating properties 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-11) and the liquid crystal alignment agent (S-12) were used respectively. A friction FFS type liquid crystal display element or liquid crystal cell was manufactured in the same manner, and various evaluations were performed. These 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 formula composition was changed as described in Table 1 below. Furthermore, liquid crystal alignment agent (S-13) is mainly used to manufacture PSA type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agents

Except using the liquid crystal alignment agent (S-13), the inkjet coating properties and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1. These results are shown in Table 2 below.

3. Preparation of liquid crystal composition

To 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck), 5 mass % of the liquid crystal compound represented by the following formula (L1-1) and 0.3 mass % of the following formula (L2- 1) and mix the photopolymerizable compounds to obtain liquid crystal composition LC1.

4. Manufacturing of PSA type liquid crystal display elements

Except using the liquid crystal alignment agent (S-13), a pair (2 pieces) of substrates with a liquid crystal alignment film were obtained in the same method as described in "4. Manufacturing of a vertical alignment liquid crystal display element" of Example 1 . Next, a liquid crystal cell was manufactured in the same manner as in Example 1, except that the liquid crystal composition LC1 prepared as described above was used instead of MLC-6608 and that a polarizing plate was not bonded. Next, the obtained liquid crystal cell was irradiated with an ultraviolet irradiation device using a metal halide lamp as a light source at an irradiation dose of 50,000 J/m ² while applying AC 10 V with a frequency of 60 Hz between the electrodes and driving the liquid crystal. UV rays. In addition, the said irradiation dose is the value measured using the light quantity meter which measured based on the wavelength of 365 nm. Furthermore, the polarizing plates of the two polarizing plates are bonded to both outer surfaces of the substrate so that the polarizing directions of the two polarizing plates are orthogonal to each other, thereby manufacturing a liquid crystal display element.

5. Evaluation of PSA type liquid crystal display elements

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1, except that a PSA-type liquid crystal display element or liquid crystal cell produced according to the method described in 4. above was used. These results are shown in Table 2 below.

[Example 14, Example 15, Example 25, Example 27]

Liquid crystal alignment agents were prepared in the same manner as in Example 1 except that the formula composition was changed as described in Table 1 below. In addition, except using each 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, and a PSA-type liquid crystal display element or liquid crystal cell was manufactured in the same manner as in Example 14. Make various evaluations. These 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 formula composition was changed as described in Table 1 below. Furthermore, liquid crystal alignment agent (S-16) is mainly used to manufacture light vertical alignment type liquid crystal display elements.

2. Evaluation of liquid crystal alignment agents

Except using the liquid crystal alignment agent (S-16), the inkjet coating properties and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1. These results are shown in Table 2 below.

3. Manufacturing of optical vertical alignment liquid crystal display elements

The same procedure as in Example 1 was performed except that the liquid crystal alignment agent (S-16) was used and the film was irradiated with polarized ultraviolet light using an Hg-Xe lamp and a glan-taylor prism instead of the rubbing treatment. An optical vertical alignment liquid crystal display element was manufactured by the same method as described in "4. Manufacturing of vertical alignment liquid crystal display element". Furthermore, polarized ultraviolet rays were irradiated from a direction tilted 40° from the normal line of the substrate, the irradiation amount was set to 200 J/m ² , and the polarization direction was set to p-polarized light. The irradiation dose is a value measured using a light meter that measures based on a wavelength of 313 nm.

4. Evaluation of optical vertical alignment type liquid crystal display elements

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1, except that a light vertical alignment type liquid crystal display element or liquid crystal cell produced according to the method described in 3. above was used. These results are shown in Table 2 below.

[Example 17 and Example 18]

Liquid crystal alignment agents were prepared in the same manner as in Example 1 except that the formula composition was changed as described in Table 1 below. In addition, except using each 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, and a light vertical alignment type liquid crystal display element or liquid crystal cell was produced in the same manner as in Example 18. , evaluate the post-bake margin, AC afterimage characteristics and DC afterimage characteristics. These 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 formula composition was changed as described in Table 1 below. Furthermore, liquid crystal alignment agent (S-19) is mainly used to manufacture light-level liquid crystal display elements.

2. Evaluation of liquid crystal alignment agents

Except using the liquid crystal alignment agent (S-19), the inkjet coating properties and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1. These results are shown in Table 2 below.

3. Manufacturing of optical FFS type liquid crystal display elements

The liquid crystal alignment agent (S-19) was used, and instead of the rubbing treatment, the film was irradiated with polarized ultraviolet light using an Hg-Xe lamp and Glan-Taylor phosphorus. An optical FFS type liquid crystal display element was produced using the same method as described in "Manufacturing of Liquid Crystal Display Element". Furthermore, polarized ultraviolet rays were irradiated from the direction perpendicular to the substrate, the irradiation amount was set to 10,000 J/m ² , and the polarizing direction was set to be a direction orthogonal to the direction of the rubbing treatment in Example 10. The irradiation dose is a value measured using a light meter based on a wavelength of 254 nm.

4. Evaluation of optical FFS type liquid crystal display elements

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1, except that an optical FFS type liquid crystal display element or liquid crystal cell produced according to the method described in 3. above was used. These results are shown in Table 2 below.

[Example 20~Example 24]

Liquid crystal alignment agents were prepared in the same manner as in Example 1 except that the formula composition was changed as described in Table 1 below. In addition, except using each 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, and an optical FFS type liquid crystal display element or liquid crystal cell was manufactured in the same manner as in Example 21. and conduct various evaluations. These 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 formula composition was changed as described in Table 1 below. Furthermore, liquid crystal alignment agent (S-26) mainly Used to manufacture TN mode liquid crystal display elements.

2. Evaluation of liquid crystal alignment agents

Except using the liquid crystal alignment agent (S-26), the inkjet coating properties and the long-term stability of the inkjet head were evaluated in the same manner as in Example 1. These results are shown in Table 2 below.

3. Manufacturing of TN-type liquid crystal display elements

Use liquid crystal alignment agent (S-26), use a rubbing machine with a roller wrapped with rayon cloth, and perform rubbing treatment under the conditions of roller rotation speed of 500 rpm, platform moving speed of 3 cm/second, and wool pressing length of 0.4 mm, except Except for this, a pair (2 pieces) of substrates having a liquid crystal alignment film was obtained in the same manner as described in "4. Production of Vertical Alignment Type Liquid Crystal Display Element" of Example 1. Next, a positive type liquid crystal (MLC-6221 manufactured by Merck) was used instead of MLC-6608. When a pair of substrates were overlapped, the rubbing directions of the respective substrates were orthogonal to each other, and the polarization directions of the two polarizing plates became A TN-type liquid crystal display element was manufactured in the same manner as in Example 1 except for the direction parallel to the rubbing direction of each substrate.

4. Evaluation of TN-type liquid crystal display elements

The post-baking margin, AC afterimage characteristics, and DC afterimage characteristics were evaluated in the same manner as in Example 1, except that a TN-type liquid crystal display element or liquid crystal cell produced according to the method described in 3. above was used. These results are shown in Table 2 below.

[Table 1]

In Table 1, the numerical values of the polymer components represent the compounding ratio (parts by mass) of each polymer relative to a total of 100 parts by mass of the polymer components used in the preparation of the liquid crystal alignment agent. The numerical value of the solvent composition is expressed relative to the total amount of solvents (compound [A], solvent [B] and other solvents) used in the preparation of the liquid crystal alignment agent. The proportion (mass ratio) of each compound. The abbreviations of the compounds are as follows.

(Compound [A])

a: 3-phenylpropan-1-ol

b: 2-phenylethan-1-ol

c: phenylmethanol

d: Anisole

e: Ethoxybenzene

f: propoxybenzene

g: 2-furylmethanol

h: 2-furyl ethanol

i: 2-furylpropanol

(Solvent [B] and other solvents)

L: Propyl carbonate

m: 4-phenylbutan-1-ol

n: butoxybenzene

o: 2-furylbutanol

p: γ-butyrolactone

q: dimethyl imidazolinone

r: N-methyl-2-pyrrolidinone

s: Butyl cellosolve

t: diacetone alcohol

u: Diethylene glycol diethyl ether

v: N-ethyl-2-pyrrolidinone

w: phenol

x: phenyl acetate

As can be seen from Table 2, Examples 1 to 27 containing compound [A] have a good balance of various characteristics such as inkjet coating properties, long-term stability of the inkjet head, post-bake margin, and afterimage characteristics. has been improved. In contrast, examples in which compound [A] is not included and NMP, γ-butyrolactone, dimethylimidazolidone, phenol, and phenyl acetate are included instead (Comparative Examples 1 to 3, Comparative Examples 8 to Comparative Examples In 9), the long-term stability of the inkjet head is worse than that of the example. In addition, in the examples (Comparative Examples 4 to 7) in which compound [A] is not included and propylene carbonate, 4-phenylbutan-1-ol, butoxybenzene, and 2-furylbutanol are included instead. , the inkjet coating property is worse than that of the example.

From the above results, it was clarified that the liquid crystal alignment agent containing the compound [A] has good coating properties on the substrate, is less likely to cause deterioration of the inkjet head, and can obtain a liquid crystal element with excellent afterimage characteristics. In addition, it was found that this liquid crystal alignment agent can also achieve a good post-baking margin.

Claims (5)

A liquid crystal alignment agent containing: a polymer component; and a compound [A] represented by the following formula (1); (R ² )x-Ar ¹ -R ¹ ... (1) (in formula (1) , Ar ¹ is an aromatic ring group with (x+1) valence, R ² is an alkyl group with 1 to 3 carbon atoms, a hydroxyalkyl group with 1 to 3 carbon atoms, or an alkoxy group with 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), wherein the compound [A] is selected from the compounds represented by the following formula (1-2) and At least one member of the group consisting of compounds represented by the following formula (1-3);

(In formula (1-2) and formula (1-3), r is an integer from 1 to 3, m is an integer from 0 to 2; R ³ is an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. A hydroxyalkyl group or an alkoxy group having 1 to 3 carbon atoms, y is 0 or 1), wherein the content ratio of the compound [A] is 10 mass relative to the total amount of solvent contained in the liquid crystal alignment agent % or more, wherein the content ratio of the compound [A] is more than 100 parts by mass relative to 100 parts by mass of the total amount of the polymer component contained in the liquid crystal alignment agent, and it contains a polyamide selected from the group consisting of At least one of the group consisting of polyamide esters, polyimides, polyorganosiloxanes, polyamides, and polymers having structural units derived from monomers having polymerizable unsaturated bonds. One serves as the polymer component. The liquid crystal alignment agent described in item 1 of the patent application includes: solvent B, which is at least one selected from the group consisting of ether solvents, alcohol solvents, chain ester solvents and ketone solvents. A method of manufacturing a liquid crystal element, which is a method of manufacturing a liquid crystal element including a liquid crystal alignment film, and uses the liquid crystal alignment agent as described in item 1 or 2 of the patent application to form the liquid crystal alignment film. A liquid crystal alignment film is formed using the liquid crystal alignment agent described in item 1 or 2 of the patent application scope. A liquid crystal element includes the liquid crystal alignment film described in item 4 of the patent application scope.