KR20220056789A - Liquid crystal aligning agent, liquid crystal alignment film and method for manufacturing same, and liquid crystal device and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal aligning agent that is excellent in storage stability and can form a liquid crystal aligning film with good reworkability and good liquid crystal alignment. The liquid crystal aligning agent comprises (A) component, (B) component, and (C) component. (A) is a polymer; (B) is a compound (where the (A) component is excluded) having two or more nucleophilic functional groups or acidic functional groups in one molecule and one or more of the nucleophilic functional groups or acidic functional groups present in one molecule having a partial structure [T] in which a nitrogen atom, a sulfur atom, or an oxygen atom is bonded to a releasable group that is releasable by at least one of heat and light; and (C) is a compound (where the (A) component and a compound having a radically polymerizable carbon-carbon double bond are excluded) having two or more electrophilic functional groups in one molecule.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, its manufacturing method, and a liquid crystal element, and its manufacturing method

TECHNICAL FIELD This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, and the manufacturing method of a liquid crystal element.

A liquid crystal element is equipped with the liquid crystal aligning film which has a function which orientates the liquid crystal molecule in a liquid crystal layer in a fixed direction. A liquid crystal aligning film is generally formed on a board|substrate by apply|coating the liquid crystal aligning agent in which a polymer component melt|dissolves in the organic solvent to the board|substrate surface, Preferably it heats.

In recent years, large-screen and high-definition liquid crystal TVs are the main components, and small display terminals such as smart phones and tablet PCs have been popularized, and the demand for higher quality of liquid crystal elements is further increasing. In view of this point, in order to improve the performance of a liquid crystal aligning film and to make it excellent in the various characteristics of a liquid crystal element, various liquid crystal aligning agents are proposed (for example, refer patent document 1). It is disclosed by patent document 1 that a liquid crystal aligning agent contains the compound which has the structure which the methylol group couple|bonded with the aromatic ring as a crosslinking agent with a polyimide or a polyimide precursor.

International Publication No. 2010/074269

High functionalization of a liquid crystal aligning film WHEREIN: It can be said that use of a crosslinking agent is an effective means. On the other hand, when the liquid crystal aligning film is peeled from the board|substrate in the manufacturing process of a liquid crystal element and reused (rework) a board|substrate by densification of the film|membrane by use of a crosslinking agent, there is concern that it becomes difficult to peel a liquid crystal aligning film from a board|substrate do.

In addition, in the liquid crystal aligning agent requiring thin film formation, storage stability is important in order to ensure the driving characteristic of a manufacturing panel. However, in the liquid crystal aligning agent using a crosslinking agent, the reliability of the liquid crystal aligning film obtained, and the storage stability of a liquid crystal aligning agent exist in the relationship of a trade-off. As a crosslinking agent mix|blended with a liquid crystal aligning agent from a viewpoint of attaining further quality improvement of a liquid crystal element, it is stable at storage temperature, and the compound which expresses high crosslinking efficiency at the time of film formation is calculated|required. Moreover, in the liquid crystal aligning agent containing a crosslinking agent, it is also pointed out that disorder of the orientation direction of the liquid crystal aligning film formed is easy to produce.

This invention is made|formed in view of the said subject, It is excellent in storage stability, and its main object is to provide the liquid crystal aligning agent which can form the liquid crystal aligning film with good rework property and liquid-crystal orientation.

According to the present invention, the following means are provided.

[1] Liquid crystal aligning agent containing following (A) component, (B) component, and (C)component.

(A) polymer

(B) having two or more nucleophilic functional groups or acidic functional groups in one molecule, and at least one of the nucleophilic functional groups or acidic functional groups present in one molecule, nitrogen atom, sulfur atom or oxygen atom , a compound having a partial structure [T] to which a leaving group detached by at least one of heat and light is bonded (however, the component (A) is excluded.)

(C) A compound having two or more spherical functional groups in one molecule (However, the component (A) and the compound having a radically polymerizable carbon-carbon double bond are excluded.)

[2] A liquid crystal aligning film formed using the liquid crystal aligning agent of [1] above.

[3] A liquid crystal element provided with the liquid crystal aligning film of the above [2].

[4] the step of applying the liquid crystal aligning agent of [1] on each of the conductive films of the pair of substrates having the conductive film to form a coating film; A method of manufacturing a liquid crystal device, comprising: constructing a liquid crystal cell by arranging the coating layers to face each other with a liquid crystal layer interposed therebetween; and irradiating light to the liquid crystal cell while a voltage is applied between the conductive layers.

According to the liquid crystal aligning agent of this invention, it is excellent in storage stability and can form a liquid crystal aligning film with favorable rework property and liquid-crystal orientation by containing (B) component and (C)component with a polymer component.

(Form for implementing the invention)

≪Liquid crystal aligning agent≫

The liquid crystal aligning agent of this indication contains the following (B) component and (C)component as a crosslinking agent while containing a polymer as (A) component.

(B) component: having two or more nucleophilic functional groups or acidic functional groups in one molecule, and at least one of the nucleophilic functional groups or acidic functional groups present in one molecule, a nitrogen atom, a sulfur atom or an oxygen atom, and heat and A compound having a partial structure [T] to which a leaving group detached by at least one of light is bonded (however, the component (A) is excluded.)

Component (C): A compound having two or more ballistic functional groups in one molecule (however, the component (A) and the compound having a radically polymerizable carbon-carbon double bond are excluded.)

Each component contained in a liquid crystal aligning agent below and the other component mix|blended arbitrarily as needed is demonstrated.

In addition, in this specification, a "hydrocarbon group" is a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. However, saturated or unsaturated may be sufficient. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be constituted by only the aromatic ring structure, and a chain structure or a structure of an alicyclic hydrocarbon may be included in a part thereof.

<(A) component: polymer component>

The main skeleton of the polymer component contained in a liquid crystal aligning agent is not specifically limited. Examples of the polymer component include polyamic acid, polyamic acid ester, polyimide, polyamine, polyenamine, polyorganosiloxane, polyester, polyamide, polyamideimide, polystyrene, polybenzoxazole precursor, polybenzoxazole. , a cellulose derivative, polyacetal, polymaleimide, styrene-maleimide-based copolymer, or poly(meth)acrylate as a main skeleton, and a functional group that reacts (crosslinking reaction) with compounds [B] and [C] polymers having In addition, (meth)acrylate means an acrylate and a methacrylate. Polyenamine is a polymer which has a carbon-carbon double bond in the position adjacent to the amino group of polyamine, For example, polyenamino ketone, polyenamino ester, polyenaminonitrile, polyenaminosulfonyl, etc. are mentioned.

As the polymer component, among them, from the viewpoint of obtaining a liquid crystal element having more excellent liquid crystal orientation and electrical properties, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and a monomer having a polymerizable unsaturated bond. It is preferable that it is at least 1 sort(s) chosen from the group which consists of a polymer (henceforth "polymer (Pm)") which has a partial structure. Among these, since the reliability of the liquid crystal element obtained is high, it is especially the liquid crystal aligning agent of this indication containing at least 1 sort(s) of polymer chosen from the group which consists of a polyamic acid, polyamic acid ester, and a polyimide as a polymer component. desirable.

Next, the preferable example of the polymer contained in the liquid crystal aligning agent of this indication is demonstrated.

(polyamic acid)

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

・Tetracarboxylic acid dianhydride

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Specific examples thereof include 1,2,3,4-butanetetracarboxylic dianhydride and the like as aliphatic tetracarboxylic dianhydride;

As alicyclic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3 ,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan- 1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1 ,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride My back;

As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroiso propylidene) diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, and the like; In addition to being mentioned respectively, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. As tetracarboxylic dianhydride, 1 type can be used individually or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis|combination of a polyamic acid can make the solubility of a polymer high, and an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarbon from the point which can obtain the liquid crystal aligning film which shows favorable electrical properties. It is preferable that at least 1 sort(s) chosen from the group which consists of acid dianhydrides is included, and it is more preferable that alicyclic tetracarboxylic dianhydride is included. The amount of the alicyclic tetracarboxylic dianhydride used is preferably 20 mol% or more, more preferably 40 mol% or more, and 50 mol% or more, based on the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid. more preferably.

・Diamine compound

A well-known compound can be used as a diamine compound used for the synthesis|combination of polyamic acid. Examples of the diamine compound include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane.

Examples of the diamine compound used for the synthesis of polyamic acid include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like as aliphatic diamine; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and the like;

As aromatic diamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-amino Phenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]hexane diacid, 2 ,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoro Methyl)-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(piperidin-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4, Main chain diamines such as 4'-diaminostilbenzene and 1,4-bis(4-aminophenyl)-piperazine:

Dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, pentadecane Oxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholesta Nyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5- Diaminobenzoic acid lanostanyl, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy) Cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestane-3 -Day, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, *-COO-, or *-OCO- (where "*" is a bond with the diaminophenyl group side) R ^I is an alkanediyl group having 1 to 3 carbon atoms R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms R ^III is an alkyl group having 1 to 20 carbon atoms, alkoxy a group, a fluoroalkyl group, or a fluoroalkoxy group. a is 0 or 1. b is an integer from 0 to 3. c is an integer from 0 to 2. d is 0 or 1. provided that 1≤a+b+c ≤3.)

side chain diamines such as compounds represented by ;

As the diaminoorganosiloxane, for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and the like; In addition to being mentioned respectively, the diamine of Unexamined-Japanese-Patent No. 2010-97188 can be used. Synthesis of polyamic acid WHEREIN: As a diamine compound, 1 type can be used individually or in combination of 2 or more type.

Synthesis of polyamic acid

A polyamic acid can be obtained by making the above tetracarboxylic dianhydride and a diamine compound react with a molecular weight modifier as needed. The ratio of using the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride groups of the tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine compound. . Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. and the like. It is preferable that the usage-rate of a molecular weight modifier shall be 20 mass parts or less with respect to a total of 100 mass parts of the tetracarboxylic dianhydride and diamine compound to be used.

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

Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphor. At least one selected from the group consisting of triamide, m-cresol, xylenol and halogenated phenol is used as the solvent, or at least one of these and another organic solvent (eg, butylcellosolve, di It is preferable to use a mixture with ethylene glycol diethyl ether, etc.). It is preferable that the usage-amount (a) of an organic solvent sets it as the quantity from which the total amount (b) of tetracarboxylic dianhydride and diamine will be 0.1-50 mass % with respect to the total amount (a+b) of a reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

(polyamic acid ester)

The polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine compound, [III] tetracarboxylic acid It can be obtained by the method of making a diester dihalide and a diamine compound react, etc. The polyamic acid ester made to contain in a liquid crystal aligning agent may have only a amic-acid ester structure, and the partial esterified thing in which a amic-acid structure and a amic-ester structure coexist may be sufficient as it. The reaction solution formed by dissolving polyamic acid ester may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid ester contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

(Polyimide)

The polyimide can be obtained, for example, by imidizing the polyamic acid synthesized as described above by dehydration and ring closure. The polyimide may be a complete imidized product in which all of the amic acid structures of the polyamic acid, which is its precursor, have been cyclized by dehydration, or may be a partial imidized product in which only a part of the amic acid structure is cyclized by dehydration and coexisting with a amic acid structure and an imide ring structure. good. It is preferable that the imidation rate is 20 to 99 %, and, as for the polyimide used for preparation of a liquid crystal aligning agent, it is more preferable that it is 30 to 90 %. This imidation ratio represents the ratio of the number of imide ring structures with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures in percentage. Here, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of polyamic acid is preferably performed by dissolving polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring closure catalyst to this solution, and heating as necessary. In this method, as a dehydrating agent, acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used, for example. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles with respect to 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst to be used is preferably 0.01 to 10 moles with respect to 1 mole of the dehydrating agent to be used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours. The reaction solution containing the polyimide obtained by the said reaction may be used for preparation of a liquid crystal aligning agent as it is, and after isolating a polyimide, you may provide for preparation of a liquid crystal aligning agent. A polyimide can also be obtained by imidation of polyamic acid ester.

It is preferable that the solution viscosity of polyamic acid, polyamic acid ester, and polyimide contained in a liquid crystal aligning agent is what has a solution viscosity of 10-800 mPa*s, when it is set as the solution with a density|concentration of 10 mass %, 15-500 mPa*s It is more preferable to have a solution viscosity of In addition, the solution viscosity (mPa·s) is a polymer solution having a concentration of 10% by mass prepared using a good polymer solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) , It is the value measured in 25 degreeC using the E-type rotational viscometer.

The weight average molecular weight (Mw) of polyamic acid, polyamic acid ester, and polyimide in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 5,000 to 100,000. The molecular weight distribution (Mw/Mn) represented by ratio of Mw and the number average molecular weight (Mn) of polystyrene conversion measured by GPC becomes like this. Preferably it is 15 or less, More preferably, it is 10 or less.

(Polyorganosiloxane)

The polyorganosiloxane contained in a liquid crystal aligning agent can be obtained by hydrolyzing and condensing a hydrolysable silane compound, for example. As a hydrolysable silane compound, For example, Alkoxysilane compounds, such as tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane; Alkoxysilane compounds containing nitrogen and sulfur, such as 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(3-cyclohexylamino)propyltrimethoxysilane ; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc. of epoxy group-containing silane compounds; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, p-styryltri unsaturated bond-containing alkoxysilane compounds such as methoxysilane; Trimethoxysilylpropyl succinic anhydride etc. are mentioned. A hydrolysable silane compound can be used individually by 1 type in these or in combination of 2 or more type. In addition, "(meth)acryloxy" is a meaning including "acryloxy" and "methacryloxy."

Said hydrolysis/condensation reaction can be performed by making 1 type, or 2 or more types of the above-mentioned silane compound and water, Preferably, it reacts in presence of a suitable catalyst and organic solvent. At the time of reaction, Preferably the usage-rate of water is 1-30 mol with respect to 1 mol of silane compounds (total amount). As a catalyst to be used, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. Although the usage-amount of a catalyst changes with reaction conditions, such as a kind of catalyst, temperature, etc., and should be set suitably, For example, with respect to the total amount of a silane compound, Preferably it is 0.01-3 times mole. Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. To [ the usage ratio of an organic solvent / 100 mass parts in total of the silane compound used for reaction ], Preferably it is 10-10,000 mass parts.

The hydrolysis/condensation reaction described above is preferably performed by heating, for example, in an oil bath or the like. In that case, the heating temperature is preferably 130°C or less, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the target polyorganosiloxane can be obtained by removing the solvent after drying the organic solvent layer separated from the reaction solution with a desiccant if necessary. In addition, the synthesis method of polyorganosiloxane is not limited to the said hydrolysis/condensation reaction, For example, you may carry out by the method of making a hydrolysable silane compound react in presence of oxalic acid and alcohol, etc.

With respect to polyorganosiloxane, it is preferable to exist in the range of 100-50,000, and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC, it is more preferable to exist in the range of 200-10,000.

(Polymer (Pm))

As a monomer which has a polymerizable unsaturated bond used for the synthesis|combination of a polymer (Pm), the compound which has a (meth)acryloyl group, a vinyl group, a vinylphenyl group, a maleimide group, etc. is mentioned, for example. Moreover, as a polymer (Pm), at least 1 sort(s) selected from the group which consists of poly(meth)acrylate, a maleimide-type polymer, and a styrene- maleimide-type copolymer from the point which can form the liquid crystal aligning film excellent in liquid-crystal orientation. can be preferably used.

Specific examples of the monomer having a polymerizable unsaturated bond include unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid: alkyl (meth)acrylate (for example, (meth)methyl acrylate, ( (meth)acrylic acid-2-ethylhexyl, etc.), (meth)acrylic acid cycloalkyl, (meth)acrylic acid benzyl, (meth)acrylic acid trimethoxysilylpropyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid glycyryl acid Unsaturated carbonic acid esters such as dil, (meth)acrylic acid 3,4-epoxycyclohexylmethyl, (meth)acrylic acid 3,4-epoxybutyl, and (meth)acrylic acid 4-hydroxybutylglycidyl ether: maleic anhydride, etc. of unsaturated polycarboxylic acid anhydrides: (meth)acrylic compounds such as;

aromatic vinyl compounds such as styrene, methylstyrene, divinylbenzene and 4-(glycidyloxymethyl)styrene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene;

N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, 4-(2,5-dioxo-3-pyrrolin-1-yl)benzoic acid, N-(4-glycidyloxyphenyl) ) maleimide, N-glycidylmaleimide, 3-maleimidebenzoic acid, 3-maleimidepropionic acid, 3-(2,5-dioxo-3-pyrrolin-1-yl)benzoic acid and 4-(2 Maleimide compounds, such as a 5-dioxo-3-pyrrolin-1-yl) methyl benzoate, are mentioned. Moreover, as a monomer which has a polymerizable unsaturated bond, the compound which has a photo-alignment group can also be used. As a monomer which has a polymerizable unsaturated bond, 1 type can be used individually or in combination of 2 or more type.

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

It is preferable that it is 250-500,000, and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC with respect to a polymer (Pm), it is more preferable that it is 500-100,000.

When providing liquid-crystal orientation ability using the photo-alignment method with respect to the organic film formed using the liquid crystal aligning agent, a photo-alignment film can be obtained by making at least one part of a polymer component into the polymer which has a photo-alignment group. A photoalignable group means the functional group which can provide anisotropy to a film|membrane by photoreactions, such as a photoisomerization reaction by light irradiation, a photodimerization reaction, an optical Fries potential reaction, or a photolysis reaction.

Specific examples of the photo-aligning group include, for example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, chalcone or its A chalcone-containing group containing a derivative as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, cyclobutane or a derivative thereof as a basic skeleton cyclobutane-containing structure, a stilbene-containing group having stilbene or a derivative thereof as a basic skeleton, and a phenylbenzoate-containing group containing phenylbenzoate or a derivative thereof as a basic skeleton thereof. Among these, the photo-aligning group is preferably at least one selected from the group consisting of an azobenzene-containing group, a cinnamic acid structure-containing group, a chalcone-containing group, a stilbene-containing group, a cyclobutane-containing structure, and a phenylbenzoate-containing group, It is especially preferable that it is a cinnamic-acid structure containing group or a cyclobutane containing structure from the point with high sensitivity to and from the point which it is easy to introduce|transduce into a polymer.

The polymer having a photo-aligning group is, for example, (1) a method of polymerization using a monomer having a photo-aligning group, (2) synthesizing a polymer having an epoxy group in a side chain, and an epoxy group-containing polymer obtained by the synthesis and photo It can be obtained by the method of making the carboxylic acid which has an orientation group react, etc. The content rate of the photo-alignment group in a polymer can be suitably set according to the kind of photo-alignment group so that desired liquid-crystal orientation ability may be provided with respect to a coating film. For example, in the case of a cinnamic acid structure-containing group, it is preferable to make the content rate of a photo-alignment group into 5 mol% or more with respect to all the structural units of the polymer which has a photo-alignment group, and it is more preferable to set it as 10-60 mol%. desirable. When a photo-aligning group is a cyclobutane containing structure, it is preferable to make the content rate of a photo-aligning group into 50 mol% or more with respect to all the structural units of the polymer which has a photo-alignment group, and it is more preferable to set it as 80 mol% or more. In addition, as a polymer which has a photo-alignment group, 1 type may be used individually, and you may use it in combination of 2 or more type.

Although single 1 type may be sufficient as the polymer component made to contain in a liquid crystal aligning agent, multiple types may be sufficient as it. For example, a 1st polymer and a 2nd polymer with higher polarity than a 1st polymer are made to contain in a liquid crystal aligning agent. In this case, it is preferable at the point which becomes possible for the 2nd polymer with high polarity to be unevenly distributed in the lower layer, and the 1st polymer to be unevenly distributed to the upper layer, and to generate|occur|produce a phase separation. As a preferable aspect of the polymer component of a liquid crystal aligning agent, the following (I) - (III) are mentioned.

(I) An aspect in which the first polymer and the second polymer are polymers selected from the group consisting of polyamic acids, polyamic acid esters and polyimides.

(II) An aspect in which one of the first polymer and the second polymer is one type of polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and the other is polyorganosiloxane.

(III) An embodiment in which one of the first polymer and the second polymer is at least one kind of polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and the other is a polymer (Pm).

In the aspects of (II) and (III), the content of the total of polyamic acid, polyamic acid ester and polyimide is contained in the liquid crystal aligning agent from the viewpoint of obtaining a liquid crystal element having sufficiently high liquid crystal orientation and voltage preservation characteristics. It is preferable to set it as 20 mass % or more with respect to the total amount of a polymer component, It is more preferable to set it as 30 % by mass or more, It is still more preferable to set it as 50 to 98 mass %. At least selected from the group consisting of polyorganosiloxane, poly(meth)acrylate, and styrene-maleimide-based copolymer when imparting liquid crystal alignment ability by a photo-alignment method to an organic film formed using a liquid crystal aligning agent By making 1 type into a polymer which has a photo-alignment group, it is preferable at the point from which the oriented film which has more favorable liquid-crystal orientation is obtained.

The content rate of the polymer component in a liquid crystal aligning agent is from a viewpoint of obtaining a liquid crystal aligning film with high adhesiveness with a board|substrate with respect to the total mass (total mass of components other than the solvent of a liquid crystal aligning agent) of solid content contained in a liquid crystal aligning agent, It is preferable to set it as 50 mass % or more, It is more preferable to set it as 60 mass % or more, It is further more preferable to set it as 70 mass % or more.

<(B) component: compound [B]>

Compound [B] is a compound having two or more nucleophilic functional groups or acidic functional groups in one molecule, and at least one of nucleophilic functional groups or acidic functional groups present in one molecule is a nitrogen atom, a sulfur atom, or an oxygen atom It has a partial structure [T] in which a leaving group (hereinafter also simply referred to as a “leaving group”) which detaches by at least one of heat and light is bonded. That is, the compound [B] has one or more protected nucleophilic functional groups or acidic functional groups. In addition, compound [B] is a component different from the polymer component which is (A) component.

It is preferable that the nucleophilic functional group or acidic functional group of the compound [B] is a group that reacts with the spherophilic functional group of the compound [C] by heating (eg, heating during film formation). In addition, in compound [B], although the protected nucleophilic functional group and protected acidic functional group are not specifically limited, It is preferable that it is a group which produces|generates the group which reacts with the nucleophilic functional group which compound [C] has by heating. A plurality of nucleophilic functional groups or a plurality of acidic functional groups which compound [B] has, from the point which can make storage stability of a liquid crystal aligning agent higher, that more than half of the nucleophilic functional groups which compound [B] has are protected Preferably, it is particularly preferred that all are protected.

When compound [B] is a compound having two or more nucleophilic functional groups in one molecule (hereinafter also referred to as "compound [B1]"), compound [B1] is a compound having two or more protected nucleophilic functional groups It is preferable that it is, and especially, the compound represented by following formula (1) is preferable.

(In formula (1), X ¹ is a nitrogen atom, a sulfur atom, an oxygen atom, or a group represented by the following formula (x-1). Y ¹ is a leaving group that is released by at least one of heat and light. R ¹ is a hydrogen atom or a monovalent organic group. R ² is a k-valent organic group. k is an integer greater than or equal to 2. When X ¹ is a sulfur atom or an oxygen atom, m is 1 and n is 0 , and when X ¹ is a nitrogen atom or a group represented by the following formula (x-1), m is 1 or 2, and n is 2-m. A plurality of X ^1s in the formula are the same or different from each other. In a case where two or more Y ^{1s exist, a plurality of Y 1s are} the same or different from each other.)

(In formula (x-1), R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. “*” represents a bond. “*1” represents a bond with R ² . )

In the formula (1), when X ¹ is a group represented by the formula (x-1), the monovalent hydrocarbon group for R ³ in the formula (x-1) is an alkyl group having 1 to 10 carbon atoms, 3 carbon atoms. and a cycloalkyl group having ∼10, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, and the like. R ³ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

X ¹ is preferably a nitrogen atom, a sulfur atom, or a group represented by the formula (x-1) among the above from the viewpoint of high crosslinking reactivity, and a nitrogen atom or a group represented by the above formula (x-1) from the viewpoint of high reworkability. The group represented by 1) is more preferable.

It is preferable that Y< ¹ > is group which detach|desorbs by heat|fever. When X ¹ is a nitrogen atom or a group represented by the formula (x-1), examples of Y ¹ include a carbamate protecting group, an amide protecting group, an imide protecting group, and a sulfonamide protecting group. Among these, a carbamate-type protecting group is preferable from the viewpoint of high desorption property by heat, and specific examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, 1,1-dimethyl-2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, etc. are mentioned. Among these, a tert-butoxycarbonyl group (Boc group) is particularly preferable because it is excellent in heat release property and the amount of the compound derived from the deprotected structure can be reduced in the film.

When X ¹ is an oxygen atom or a sulfur atom, Y ¹ may be, for example, an ether protecting group such as a methyl group, an ethyl group, a tert-butyl group, a benzyl group, a p-methoxybenzyl group or a trityl group; acetal protecting groups such as a methoxymethyl group, an ethoxyethyl group, and a 2-tetrahydropyranyl group; acyl-type protecting groups, such as an acetyl group, a pivaloyl group, a benzoyl group, and a trichloroacetyl group; Allyl-type protecting groups, such as an allyl group and a methallyl group; carbamate protecting groups such as tert-butoxycarbonyl group; and silyl ether protecting groups such as trimethylsilyl group, triethylsilyl group and tert-butyldimethylsilyl group. From the viewpoint of achieving both easiness of desorption by heat and storage stability, when X ¹ is an oxygen atom or a sulfur atom, Y ¹ is an alkyl group having 1 to 7 carbon atoms, 2-tetrahydropyranyl group, methoxymethyl group, It is preferable that it is a 1-ethoxyethyl group or an acetyl group.

The monovalent organic group of R ¹ is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms. R ¹ is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The structure which does not inhibit the nucleophilicity of X< ¹ > is preferable as for the organic group of k valence of R< ² >. In R ² , the k-valent organic group preferably has 1 to 40 carbon atoms. As the k-valent organic group of R ² , a k-valent hydrocarbon group having 1 to 40 carbon atoms, -O-, -S-, -CO-, -COO-, -NR ⁴ -, - CO-NR ⁴ -, -NR ⁴ -CO-O-, -NR ⁴ -CO-NR ⁵ -, -CO-NR ⁴ -NR ⁵ - or a k-valent group comprising a heterocycle, provided that R ⁴ and R ⁵ is each independently a hydrogen atom or a monovalent organic group (the same hereinafter) and the like. Here, as a C1-C40 hydrocarbon group, a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group are mentioned. Among these, a chain|strand hydrocarbon group is preferable at the point which can form the film|membrane with higher crosslinking reactivity and high adhesiveness with a board|substrate. The monovalent organic group of R ⁴ and R ⁵ is preferably a monovalent hydrocarbon group or protecting group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group or protecting group having 1 to 6 carbon atoms, and still more preferably a monovalent hydrocarbon group or protecting group having 1 to 6 carbon atoms. -6 alkyl group or tert-butoxycarbonyl group.

It is preferable that R< ² > is a k-valent group which does not have an aromatic ring at the point which crosslinking reactivity is higher, and a favorable electrical property and a highly adhesive oriented film can be obtained. Specifically, R ² is a k-valent chain hydrocarbon group, or between carbon-carbon bonds of the chain hydrocarbon group -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO -NR ⁴ -, -NR ⁴ -CO-O-, -NR ⁴ -CO-NR ⁵ -, -CO-NR ⁴ -NR ⁵ - or a k-valent group containing a non-aromatic heterocycle is preferable. . Here, C2-C30 is preferable and, as for the chain hydrocarbon group of k valence, C3-C20 is more preferable. It is preferable that a non-aromatic heterocyclic ring is a nitrogen-containing ring, for example, a piperidine ring, a pyrrolidine ring, a hexamethyleneimine ring, a morpholine ring, an isocyanurate ring, etc. are mentioned. As a preferable specific example of R< ² >, the structure etc. which are represented by each of following formula (r-1) - formula (r-4) are mentioned, for example.

(In formulas (r-1) to (r-4), t is an integer of 0 to 18. X ² and X ³ are each independently -O-, -S-, -CO-, -COO -, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O-, -NR ⁴ -CO-NR ⁵ -, or -CO-NR ⁴ -NR ⁵ - t1, t2 and t3 are each independently an integer of 1 to 10. u is an integer of 0 to 3. R ²⁰ is a divalent group represented by the above formula (r-1) or (r-2). " indicates that it is a bond.)

When X< ¹ > is a nitrogen atom or group represented by said Formula (x-1), 1 is preferable at the point which can make rework property high, maintaining liquid-crystal orientation and an electrical property favorably.

From a viewpoint of achieving coexistence of liquid-crystal orientation and an electrical characteristic, and rework property, 2-10 are preferable, as for k, 2-6 are more preferable, 2-4 are still more preferable, 2 or 3 is especially preferable. .

With respect to compound [B1], when X ¹ is a nitrogen atom or a group represented by the formula (x-1), and the polymer component has an amino group terminal or has an amino group in a side chain, compound [B1] is a polymer It is preferable that it is a compound which shows the basicity higher than the basicity of the amino group which comprises a component. Specifically, it is preferable that the pka value of the conjugated acid of the amino group of the compound [B1] (25° C. in water) is larger than the pka value of the general aromatic diamine monomer (specifically, 4 or less), and the reaction selectivity From the viewpoint of , it is more preferable that the pka value is 6 or more (Δpka≥2). Further, when X ¹ is an oxygen atom or a sulfur atom, and the polymer component has a hydroxyl group-containing monomer, the compound [B1] is preferably a compound exhibiting an acidity lower than the acidity of the hydroxyl group-containing monomer constituting the polymer component. In general, the hydroxyl component of the polymer component is carboxylic acid (pka=4 to 5), and it is preferable that the pka values of the OH and SH groups of the compound [B1] are 6 or more (Δpka≧2). When X ¹ is an oxygen atom or a sulfur atom, it is preferable to use a base together in order to increase the reactivity of X ¹ . As a specific base, heterocyclic compounds, such as pyridine and a pyrimidine derivative, and aliphatic amines, such as triethylamine, can be used suitably.

Specific examples of the compound [B1] include compounds represented by each of the following formulas (b1) to (b13).

When the compound [B] is a compound having two or more acidic functional groups in one molecule (hereinafter also referred to as “compound [B2]”), the compound [B2] is, among others, a compound represented by the following formula (3) it is preferable

(In formula (3), X ² is a carboxylic acid group, a phosphoric acid group, a phosphorous acid group, or a sulfonic acid group. X ³ is a protected carboxylic acid group, a protected phosphoric acid group, a protected phosphorous acid group, or a protected sulfonic acid group. R ⁶ is an organic group having a valence of (i+j). i is an integer greater than or equal to 0. j is an integer greater than or equal to 1. proviso that (i+j)≥2 is satisfied. When i is greater than or equal to 2, a plurality of Xs ² is the same or different from each other. When j is 2 or more, a plurality of X ³ are the same or different from each other.)

In the formula (3), X ³ is a group formed by substituting a leaving group for a hydrogen atom of an OH group included in a carbonic acid group, a phosphoric acid group, a phosphorous acid group, or a sulfonic acid group, and has a group represented by "*-OL ¹ " ( However, L ¹ represents a leaving group, and "*" represents a bond). Specific examples of the group represented by “*-OL ¹ ” include an acetal-based protecting group and a cyclic alcohol-based protecting group, and examples include groups represented by each of the following formulas (L1-1) to (L1-8). can

(In formulas (L1-1) to (L1-8), "*" represents a bond.)

It is preferable that the (i+j) valence organic group of R ⁶ has a structure that does not inhibit the nucleophilicity of X ² and X ³ . In R ⁶ , the organic group having a valence of (i+j) preferably has 1 to 40 carbon atoms. Examples of the (i+j) valence organic group of R ⁶ include a hydrocarbon group having 1 to 40 carbon atoms (i+j), and -O-, -S-, -CO-, -COO-, -NR between the carbon-carbon bonds of the hydrocarbon group. ⁷ -, -CO-NR ⁷ -, -NR ⁷ -CO-O-, -NR ⁷ -CO-NR ⁸ -, -CO-NR ⁷ -NR ⁸ - or a (i+j) valent group containing a heterocycle ( However, R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms (the same hereinafter) and the like. The monovalent organic group of R ⁷ and R ⁸ is preferably a monovalent hydrocarbon group or protecting group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group or protecting group having 1 to 6 carbon atoms, and still more preferably a monovalent hydrocarbon group or protecting group having 1 to 6 carbon atoms. -6 alkyl group or tert-butoxycarbonyl group.

It is preferable that R< ⁶ > is a (i+j) valence group which does not have an aromatic ring at the point which crosslinking reactivity is higher and a favorable electrical property and a highly adhesive oriented film can be obtained. Specifically, R ⁶ is a chain hydrocarbon group having a valence of (i+j), or between carbon-carbon bonds of the chain hydrocarbon group -O-, -S-, -CO-, -COO-, -NR ⁷ -, -CO -NR ⁷ -, -NR ⁷ -CO-O-, -NR ⁷ -CO-NR ⁸ -, -CO-NR ⁷ -NR ⁸ - or a (i+j) valent group including a non-aromatic heterocycle, or ( It is preferable that i+j) is an alicyclic hydrocarbon group. Here, the chain hydrocarbon group having a valence of (i+j) preferably has 2 to 30 carbon atoms, and more preferably has 3 to 20 carbon atoms. It is preferable that a non-aromatic heterocyclic ring is a nitrogen-containing ring, for example, a piperidine ring, a pyrrolidine ring, a hexamethyleneimine ring, a morpholine ring, an isocyanurate ring, etc. are mentioned.

From an adhesive viewpoint of a liquid crystal aligning film, R< ⁶ > is a (i+j) valence chain hydrocarbon group, or -O-, -S-, -CO-, -COO-, -NR between carbon-carbon bonds of a chain hydrocarbon group ⁷ -, -CO-NR ⁷ -, -NR ⁷ -CO-O-, -NR ⁷ -CO-NR ⁸ -, -CO-NR ⁷ -NR ⁸ - or (i+j) including a non-aromatic heterocycle It is preferable to be a group.

Specific examples of the compound [B2] include compounds in which at least one of the acid groups of polyfunctional carboxylic acid, polyfunctional phosphoric acid, polyfunctional phosphorous acid, and polyfunctional sulfonic acid is protected. Of these, compounds in which at least one of the carboxy groups of the polyfunctional carboxylic acid are protected can be preferably used from the viewpoint of high reactivity with the compound [C].

Specific examples of the compound [B2] include fumaric acid, malonic acid, adipic acid, terephthalic acid, isophthalic acid, sebacic acid, diphenyl ether-4,4'-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, etc. a compound in which at least one of the carboxy groups of the dicarboxylic acid is protected;

At least one of the carboxyl groups of tricarboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, trimellitic acid, and 1,2,4-naphthalenetricarboxylic acid is protected compound;

Among the carboxy groups of tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, and pyromellitic acid at least one protected compound;

a compound represented by each of the following formulas (b2-1) to (b2-3); and the like.

(In formulas (b2-1) to (b2-3), a plurality of L ² are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, or a thermal leaving group. At least one of a plurality of L ² is a thermal leaving group.)

Content of the compound [B] in the liquid crystal aligning agent of this indication makes storage stability of a liquid crystal aligning agent favorable, From a viewpoint of obtaining the liquid crystal element excellent in liquid crystal orientation, an electrical property, and rework property, to a liquid crystal aligning agent 0.5 mass part or more is preferable with respect to 100 mass parts of total amounts of the contained polymer component. 1 mass part or more is more preferable with respect to 100 mass parts of total amounts of a polymer component, and, as for content of a compound [B], 2 mass parts or more are still more preferable. Moreover, from a viewpoint of suppressing the fall of rework property, 20 mass parts or less are preferable with respect to 100 mass parts of total amounts of a polymer component, and, as for content of compound [B], 15 mass parts or less are more preferable. As a compound [B], you may use individually by 1 type, and may use it in combination of 2 or more type.

<(C) component: compound [C]>

The compound [C] is a compound having two or more ballistic functional groups in one molecule (however, a compound having a radically polymerizable carbon-carbon double bond is excluded). In addition, compound [C] is a component different from the polymer component which is (A) component. The spherophilic functional group of the compound [C] is preferably a group that reacts with the nucleophilic functional group of the compound [B] by heating (eg, heating during film formation).

When the compound [B] is the compound [B1], since a liquid crystal device having high crosslinking reactivity and excellent liquid crystal orientation and electrical properties can be obtained, compound [C] is an isocyanate group, a protected isocyanate group as a spherophilic functional group A compound having at least one selected from the group consisting of a group, a cyclic carbonate group, a methylol group, a protected methylol group, a group having a ketene structure, and a group having a Meldrum acid structure (hereinafter also referred to as “compound [C1]”) ) is preferred. The electrophilic functional group of the compound [C1] is, among others, at least selected from the group consisting of an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a group having a ketene structure, and a group having a Meldrum acid structure. One type is more preferable.

The protected isocyanate group WHEREIN: It is preferable that a protecting group is a group which detach|desorbs by heat. The protected isocyanate group can be introduced into the compound by reacting the isocyanate group with a blocking agent. A known blocking agent can be used, for example, an alcohol-based compound, a phenol-based compound, an active methylene-based compound, a mercaptan-based compound, an acid amide-based compound, an acid imide-based compound, an imidazole-based compound, and a pyrazole-based compound , a urea-based compound, an oxime-based compound, an amine-based compound, an imine-based compound, and a pyridine-based compound. From the viewpoint of suppressing that the component derived from the group detached by heating during film formation remains in the film, the protecting group in the protected isocyanate group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Do.

Examples of the protecting group in the protected methylol group include the groups exemplified as Y ¹ in the case where X ¹ is an oxygen atom in compound [B1].

The number of the spinneret functional group which the compound [C1] has is preferably 2 to 10, and 2 to 8 from the viewpoint of achieving compatibility of liquid crystal orientation and electrical properties and reworkability, and from the viewpoint of suppressing a decrease in storage stability. Dogs are more preferred.

The molecular weight of the compound [C1] is preferably 1000 or less, more preferably 800 or less, and still more preferably 650 or less.

As compound [C1], the compound represented by following formula (2) can be used preferably.

(Z ¹ ) _m -R ⁶ ... (2)

(In formula (2), Z ¹ is an isocyanate group, a protected isocyanate group, a cyclic carbonate group, a methylol group, a protected methylol group, a group having a ketene structure, or a group having a Meldrum acid structure. R ⁶ is , an organic group having a valence of m. m is an integer of 2 or more.)

In the formula (2), the m-valent organic group of R ⁶ preferably has 1 to 40 carbon atoms. Examples of the m-valent organic group for R ⁶ include an m-valent hydrocarbon group having 1 to 40 carbon atoms, and at least one methylene group of the hydrocarbon group is -O-, -S-, -CO-, -COO-, -NR ⁴ -, - CO-NR ⁴ -, -NR ⁴ -CO-O-, -NR ⁴ -CO-NR ⁵ -, -CO-NR ⁴ -NR ⁵ - or an m-valent group substituted with a heterocyclic ring;

Z ¹ is preferably an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a group having a ketene structure, or a group having a Meldrum acid structure. m becomes like this. Preferably it is 2-10, More preferably, it is 2-8.

Specific examples of the compound [C1] include compounds represented by each of the following formulas (c1) to (c15).

(In formulas (c1), (c2) and (c4), R ⁷ is a protecting group. One of R ¹¹ , R ¹² and R ¹³ is a methyl group, and the rest is a hydrogen atom. R ¹⁴ , R ¹⁵ and one of R ¹⁶ is a methyl group and the rest is a hydrogen atom, one of R ¹⁷ , R ¹⁸ and R ¹⁹ is a methyl group and the rest is a hydrogen atom.)

When the compound [B] is the compound [B2], since a liquid crystal element having high crosslinking reactivity and excellent liquid crystal orientation and electrical properties can be obtained, compound [C] is a spherophilic functional group, a cyclic ether group, a cyclic carbonate It is preferable that it is a compound (hereinafter also referred to as “compound [C2]”) having at least one selected from the group consisting of a group, an oxazoline group, and a group having a β-hydroxyamide structure. Here, as a cyclic ether group, an oxiranyl group, oxetanyl group, etc. are mentioned. The group having a β-hydroxyamide structure is preferably a β-hydroxyalkylamide group.

Among these, the electrophilic functional group of the compound [C2] is preferably at least one selected from the group consisting of a cyclic ether group, a cyclic carbonate group, and a group having a β-hydroxyamide structure, a cyclic carbonate group and a β-hydroxy group At least one selected from the group consisting of a group having a hydroxyamide structure is more preferable.

The number of the spinneret functional group which the compound [C2] has is preferably 2 to 10, and 2 to 8 from the viewpoint of achieving compatibility of liquid crystal orientation and electrical properties and reworkability, and from the viewpoint of suppressing a decrease in storage stability. Dogs are more preferred.

The molecular weight of the compound [C2] is preferably 1000 or less, more preferably 800 or less, and still more preferably 650 or less.

As a preferable example of compound [C2], the compound represented by following formula (4) is mentioned.

(In formula (4), Z ¹ is a cyclic ether group, a cyclic carbonate group, an oxazoline group, and a β-hydroxyalkylamide group. R ¹⁰ is an r-valent organic group having 1 to 40 carbon atoms. r is It is an integer from 2 to 10.)

In the formula (4), as R ¹⁰ , for example, a hydrocarbon group or a group formed by substituting an arbitrary methylene group of a hydrocarbon group with -O-, -S-, -CO-, -COO-, etc. (hereinafter, "hetero atom-containing group"), a group in which arbitrary hydrogen atoms of a hydrocarbon group or a hetero atom-containing group are substituted with a hydroxyl group, a halogen atom, a cyano group, a nitro group, etc., and a group having a heterocyclic structure. there is.

It is preferable that R< ¹⁰ > is an r-valent group which does not have an aromatic ring at the point which crosslinking reactivity is higher and a favorable electrical property and a highly adhesive oriented film can be obtained. Specifically, R ¹⁰ is an r-valent chain hydrocarbon group, or contains -O-, -S-, -CO-, -COO- or a non-aromatic heterocycle between carbon-carbon bonds of the chain hydrocarbon group. It is preferable that r is a valent group. Here, C2-C30 is preferable and, as for the chain hydrocarbon group of r valence, C3-C20 is more preferable. It is preferable that a non-aromatic heterocyclic ring is a nitrogen-containing ring, for example, a piperidine ring, a pyrrolidine ring, a hexamethyleneimine ring, a morpholine ring, an isocyanurate ring, etc. are mentioned. As a preferable specific example of R< ¹⁰ >, the structure etc. which are represented by each of the said Formula (r-1) - Formula (r-4) are mentioned, for example.

Specific examples of the compound [C2] include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether as a compound having a cyclic ether group. , Glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexane Diol, N,N,N',N'-tetraglycidyl-p-phenylenediamine, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N ,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4 '-Diaminobiphenyl, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidyl) Aminomethyl) cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-4,4 '-diaminodiphenylpentane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, N,N ,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, 1,4-bis(N,N- Diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane and compounds represented by each of the following formulas (c2-1) to (c2-9).

(In formula (c2-5), a is an integer of 1-3.)

Specific examples of the compound having a cyclic carbonate group include compounds represented by each of the following formulas (c2-10) to (c2-16).

(in formula (c2-16), b is an integer of 1-10.)

Specific examples of the compound having an oxazoline group or a protected oxazoline group (β-hydroxyamide group) include compounds represented by each of the following formulas (c2-17) to (c2-21). there is.

Content of the compound [C] in the liquid crystal aligning agent of this indication is 0.5 mass with respect to 100 mass parts of whole amounts of the polymer component contained in a liquid crystal aligning agent from a viewpoint of obtaining the liquid crystal element excellent in liquid-crystal orientation and an electrical property More than one part is preferable. 1 mass part or more is more preferable with respect to 100 mass parts of total amounts of a polymer component, and, as for content of a compound [C], 2 mass parts or more are more preferable. Moreover, from a viewpoint of suppressing the fall of rework property, 20 mass parts or less are preferable with respect to 100 mass parts of total amounts of a polymer component, and, as for content of compound [C], 15 mass parts or less are more preferable. As a compound [C], you may use individually by 1 type, and may use it in combination of 2 or more type.

20-500 mass parts of compound [C] are preferable with respect to 100 mass parts of compound [B], and, as for the ratio of compound [B] and compound [C] in a liquid crystal aligning agent, 30-300 mass parts is more preferable. In addition, the total amount of a compound [B] and a compound [C] is 1 mass part or more with respect to 100 mass parts of total amounts of the polymer component contained in a liquid crystal aligning agent from a viewpoint of fully obtaining the improvement effect of liquid-crystal orientation and an electrical property. This is preferable, 2 mass parts or more are more preferable, and 5 mass parts or more are still more preferable. On the other hand, the total amount of compound [B] and compound [C] is preferably 40 parts by mass or less, and 30 parts by mass or less from the viewpoint of suppressing the decrease in reworkability with respect to 100 parts by mass of the total amount of the polymer component. is more preferable.

The combination of the compound [B] and the compound [C] is not particularly limited, and any one or more kinds of the aforementioned compound [B] and any one or more kinds of the compound [C] can be used in appropriate combination. From the viewpoint of advancing the crosslinking reaction to improve the liquid crystal orientation and electrical properties of the obtained liquid crystal element, compound [B1] and compound [C1] are used in combination, or compound [B2] and compound [C2] are used in combination It is preferable to do

When compound [B1] and compound [C1] are used in combination, the compound [B1] and the compound from the viewpoint of improving the liquid crystal orientation and electrical properties of the obtained liquid crystal element while ensuring reworkability with an appropriate crosslinking density Only any one of [C1] is a moiety different from the protected nucleophilic functional group (specifically, R ¹ and R ² in the formula (1)), or a different moiety from the protected nucleophilic functional group (specifically, R 1 and R 2 ) , R ⁶ ) in the formula (2) does not have a benzene ring, a naphthalene ring, a cyclohexane ring and an isocyanurate ring, or neither compound [B] nor compound [C] has protected nucleophilicity It is preferable not to have any of a benzene ring, a naphthalene ring, a cyclohexane ring, and an isocyanurate ring in a part different from a functional group and a part different from the protected spinneret functional group. Among these, the nucleophilic functional group protected only in either one of compound [B] and compound [C] from the viewpoint of being able to increase the degree of freedom in compound selection while maintaining a well-balanced rework property, liquid-crystal orientation, and electrical properties. It is preferable not to have at least one of a benzene ring, a naphthalene ring, a cyclohexane ring, and an isocyanurate ring in a portion different from , and a portion different from the protected orrogenic functional group.

<Other ingredients>

The liquid crystal aligning agent of this indication may further contain components (henceforth another compound) other than a polymer component, a compound [B], and a compound [C] as needed. Specific examples thereof include a functional silane compound (for example, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, etc.), an antioxidant, a metal chelate compound, curing Accelerators, surfactants, fillers, dispersants, photosensitizers, etc. are mentioned. In addition, content of other compounds is within the range which does not impair the effect of this indication, and can be suitably selected according to each compound.

(solvent)

The liquid crystal aligning agent of this indication is a polymer component, a compound [B], a compound [C], and the component mix|blended arbitrarily as needed, Preferably, it is prepared as a liquid composition melt|dissolved in the solvent. The solvent is preferably an organic solvent, and examples thereof include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons.

Specific examples of the organic solvent to be used include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, and γ-butyrolactone. , γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol monomethyl ether, butyl lactate , Butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl Ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether Methyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, ethylene carbonate, propylene carbonate, cyclohexanone, diisobutyl ketone, 3 -Methoxy-1-butanol, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Although the solid content concentration (ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies to the total mass of a liquid crystal aligning agent) in a liquid crystal aligning agent considers a viscosity, volatility, etc., and is suitably selected, Preferably it is 1-10 It is the range of mass %. The film thickness of a coating film can fully be ensured that solid content concentration is 1 mass % or more, and there exists a tendency for a favorable liquid crystal aligning film to be obtained. Moreover, when solid content concentration is 10 mass % or less, the film thickness of a coating film does not become excessively excessive, and the viscosity of a liquid crystal aligning agent can be made high suitably, and there exists a tendency which can make applicability|paintability favorable.

«Liquid crystal alignment film and liquid crystal element»

The liquid crystal aligning film of this indication is formed with the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) It can be applied to various modes such as type, FFS(Fringe Field Switching) type, OCB(Optically Compensated Bend) type, PSA(Polymer Sustained Alignment) type. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate used differs depending on the desired operation mode. Steps 2 and 3 are common to each operation mode.

<Step 1: Formation of a coating film>

First, a liquid crystal aligning agent is apply|coated on a board|substrate, Preferably a coating film is formed on a board|substrate by heating an application surface. As a board|substrate, For example, glass, such as float glass and soda glass; A transparent substrate made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly(alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Corporation in the United States) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. are used. can When manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates on which a patterned transparent conductive film is formed are used. On the other hand, when manufacturing an IPS type or FFS type liquid crystal element, the board|substrate on which the electrode patterned in comb-tooth shape is formed, and the counter board|substrate on which the electrode is not formed are used. On the electrode formation surface, application|coating of the liquid crystal aligning agent to a board|substrate becomes like this. Preferably the offset printing method, the flexographic printing method, the spin coating method, the roll coater method, or the inkjet printing method is performed.

After apply|coating a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated liquid crystal aligning agent, Preferably, preliminary heating (prebaking) is performed. Pre-baking temperature becomes like this. Preferably it is 30-200 degreeC, and pre-baking time becomes like this. Preferably it is 0.25 to 10 minutes. Then, a baking (post-baking) process is implemented for the purpose of completely removing a solvent, etc. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-250 degreeC, More preferably, it is 80-200 degreeC. Post-baking time becomes like this. Preferably it is 5 to 200 minutes. Thus, the film thickness of the film|membrane formed becomes like this. Preferably it is 0.001-1 micrometer.

<Step 2: Orientation treatment>

When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, the process (orientation process) which provides liquid-crystal orientation ability to the coating film formed in the said process 1 is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. As the alignment treatment, a rubbing treatment in which the coating film formed on the substrate is rubbed in a certain direction with a roll wound with a cloth made of, for example, nylon, rayon, or cotton fibers, or the coating film formed on the substrate is irradiated with light to give the liquid crystal A photo-alignment treatment for imparting alignment ability or the like can be used. On the other hand, in the case of manufacturing a vertical alignment (VA) type liquid crystal element, the coating film formed in step 1 can be used as it is as a liquid crystal aligning film. good. The liquid crystal aligning film suitable for the liquid crystal element of a vertical alignment type is suitable also for a PSA type liquid crystal element.

Photo-alignment treatment WHEREIN: Light irradiation is a method of irradiating with respect to the coating film after a post-baking process, the method of irradiating with respect to the coating film before a post-baking process as after a pre-baking process, A coating film in at least any of a pre-baking process and a post-baking process. It can be carried out by a method of irradiating the coating film during heating, or the like. As radiation irradiated to the coating film, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used. Preferably, it is an ultraviolet-ray containing light of a wavelength of 200-400 nm. When the radiation is polarized light, linearly polarized light or partially polarized light may be sufficient. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. In the case of non-polarized radiation, the irradiation direction is made into an oblique direction.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. are mentioned, for example. The radiation dose to the substrate surface is preferably 400 to 50,000 J/m 2 , more preferably 1,000 to 20,000 J/m 2 . After light irradiation for imparting orientation ability, the substrate surface is washed with, for example, water, an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) ) or a process for washing using a mixture thereof or a process for heating the substrate may be performed.

<Step 3: Construction of a liquid crystal cell>

Two board|substrates with a liquid crystal aligning film are prepared as mentioned above, and a liquid crystal cell is manufactured so that a liquid crystal may be arrange|positioned adjacent to a liquid crystal aligning film between two board|substrates. In order to manufacture a liquid crystal cell, for example, two board|substrates are opposingly arrange|positioned through a gap|interval so that a liquid crystal aligning film may oppose, the peripheral part of two board|substrates is joined with a sealing compound, The cell enclosed by the board|substrate surface and a sealing compound. A method of sealing an injection hole by injecting and filling a liquid crystal into a gap, a method using an ODF method, etc. are mentioned. As a sealing agent, the epoxy resin etc. containing the aluminum oxide sphere as a hardening|curing agent and a spacer can be used, for example. As a liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, Among these, a nematic liquid crystal is preferable. In the PSA mode, after the construction of the liquid crystal cell, a process of irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films included in the pair of substrates is performed.

A PSA type liquid crystal element can be manufactured by the method including the following processes.

- The process of apply|coating the liquid crystal aligning agent of this indication on each conductive film of a pair of board|substrates which has an electrically conductive film, and forming a coating film.

A process of constructing a liquid crystal cell by arranging a pair of substrates coated with a liquid crystal aligning agent so that the coating film faces each other with a liquid crystal layer interposed therebetween.

A process of irradiating light to a liquid crystal cell in a state where a voltage is applied between the conductive films.

Specifically, first, between a pair of substrates having a conductive film, a liquid crystal cell is constructed in the same manner as in Steps 1 to 3, except for injecting or dropping a photopolymerizable monomer together with a liquid crystal. A conventionally well-known compound can be used as a photopolymerizable monomer inject|poured or dripped with a liquid crystal. Preferably, it is a polyfunctional (meth)acryl monomer.

In the manufacture of a PSA type liquid crystal element, after the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light in a state in which a voltage is applied between the conductive films of a pair of substrates. The voltage to be applied can be, for example, 5 to 50 V of direct current or alternating current. As the light to be irradiated, for example, ultraviolet light and visible light containing light having a wavelength of 150 to 800 nm can be used. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. The amount of light irradiated is preferably 1,000 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 .

With respect to the liquid crystal cell of each mode, a polarizing plate is joined to the outer surface of a liquid crystal cell successively as needed, and it is set as a liquid crystal element. As a polarizing plate, the polarizing plate which sandwiched the polarizing film called "H film" which absorbed iodine while extending|stretching orienting polyvinyl alcohol, with a cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

The liquid crystal element of the present disclosure can be effectively applied to various uses. Specifically, for example, various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, various monitors, liquid crystal TVs, information displays, and the like; , dimming film, retardation film, and the like.

[Example]

Hereinafter, although an Example demonstrates concretely, this invention is not limited to the following Example.

In the following examples, the solution viscosity of the polymer, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the imidization rate were measured by the following methods.

<Solution Viscosity of Polymer>

The solution viscosity of the polymer was measured at 25°C using an E-type viscometer.

<A weight average molecular weight and a number average molecular weight>

By gel permeation chromatography (GPC), Mw and Mn were measured under the following conditions. The molecular weight distribution (Mw/Mn) was calculated from the obtained Mw and Mn.

Device: "GPC-101" by Showa Denko Co., Ltd.

GPC column: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" manufactured by Shimadzu DLC Co., Ltd. are combined

Mobile phase: tetrahydrofuran (THF)

Column temperature: 40°C

Flow rate: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection volume: 100 μL

Detector: Differential Refractometer

Standard material: monodisperse polystyrene

<Imidation rate of polyimide>

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR measurement was performed at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the following formula (1).

Imidization ratio [%] = (1-(β ¹ /(β ² ×α))) × 100 … (One)

(In formula (1), β ¹ is the peak area derived from protons of the NH group appearing around 10 ppm of the chemical shift, β ² is the peak area derived from other protons, and α is the polymer precursor (polyamic acid) It is the ratio of the number of other protons to one proton of the NH group.)

The abbreviation of the compound used in the following example is shown below. In addition, in the following, "the compound represented by Formula (X)" may be simply represented as "Compound (X)" for convenience.

· Monomers and branched carboxylic acids

・Compound [B]

・Compound [C]

(In formulas (C-1) and (C-2), R is a tert-butoxycarbonyl group or a group derived from methylethylketoxime (*-ON=C(CH ₃ )(C ₂ H ₅ )) am.)

・Other additives

<Synthesis of polymer>

1. Synthesis of polyimide

[Synthesis Example 1]

100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, and 30 mol parts of cholestanyloxy-2,4-diaminobenzene and 30 mol parts of 3,5-diaminobenzoic acid as diamine And 40 molar parts of 4,4'- diaminodiphenylmethane were melt|dissolved in N-methyl- 2-pyrrolidone (NMP), and the solution containing 20 mass % of polyamic acids was obtained by making it react at 40 degreeC for 24 hours. . Next, NMP was added to the obtained polyamic acid solution, 3.00 molar equivalents of pyridine and acetic anhydride were added with respect to the carboxyl group of polyamic acid, and dehydration ring closure reaction was performed at 80 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone, and further concentrated, thereby containing 20% by mass of a polyimide having an imidization rate of 71% (this is referred to as a polymer (P-1)) A solution was obtained. A small amount of this solution was fractionated, and the solution viscosity measured as a solution having a concentration of 10 mass% by adding NMP was 100 mPa·s.

[Synthesis Examples 2 and 5]

The polymerization was carried out in the same manner as in Synthesis Example 1 except that the types and amounts of tetracarboxylic dianhydride and diamine used for polymerization were changed as shown in Table 1, and the polymer (P-2) or polymer (P) which is a polyimide -5) was obtained.

2. Synthesis of polyamic acid

[Synthesis Example 3]

100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, and 30 mol parts of compound (D-2), 40 mol parts of compound (D-4) as diamine, and 3,5-dia 30 mol parts of minobenzoic acid was melt|dissolved in NMP, and the solution containing 20 mass % of polyamic acids (this is called polymer (P-3)) was obtained by making it react at 40 degreeC for 24 hours. A small amount of this solution was fractionated, and the solution viscosity measured as a solution having a concentration of 10% by mass by adding NMP was 80 mPa·s.

[Synthesis Examples 4, 6-8]

Polyamic acid polymers (P-4), (P- Solutions containing each of 6) to (P-8) were obtained. In addition, polymerization is performed by matching the molar ratio of diamine and tetracarboxylic dianhydride (diamine/tetracarboxylic dianhydride) to 0.95-1.00 so that the viscosity of the NMP solution with a polymer concentration of 10 mass % becomes 80-100 mPa*s. did. In Table 1, the numerical value of an acid anhydride shows the ratio (molar part) of each compound with respect to 100 molar parts of the total amount of tetracarboxylic dianhydride used for the synthesis|combination. The numerical value of diamine shows the ratio (molar part) of each compound with respect to 100 molar parts of the total amount of diamine used for synthesis|combination.

3. Synthesis of polyorganosiloxane

[Synthesis Example 9]

90.0 g of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were put into a 1000 ml 3-neck flask, and it mixed at room temperature. Next, 100 g of deionized water was dripped from the dropping funnel over 30 minutes, and then, the reaction was performed at 80°C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass % ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure. Methyl isobutyl ketone was added in an appropriate amount, and the 50 mass % solution of the polymer (ESSQ-1) which is polyorganosiloxane which has an epoxy group was obtained.

In a 500 ml three-neck flask, 6.28 g of compound (CA-1) (20 mol% based on the amount of epoxy groups in the polymer (ESSQ-1)), 3.44 g of compound (CA-3) (epoxy of the polymer (ESSQ-1) 10 mol%), tetrabutylammonium bromide 2.00g, polymer (ESSQ-1) containing solution 80g, and methylisobutylketone 239g were added, and it stirred at 90 degreeC for 18 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. After that, the organic layer is recovered, concentration and NMP dilution are repeated twice with a rotary evaporator, and then the NMP solution of the polymer (PS-1) is adjusted so that the solid content concentration is 10% by mass using NMP. got it

[Synthesis Example 10]

NMP solution containing 10 mass % of polymer (PS-2) which is polyorganosiloxane in the same manner as in Synthesis Example 9 except that the type and amount of the side chain carboxylic acid used for the reaction were changed as shown in Table 2 got In addition, in Table 2, the numerical value of a side chain carboxylic acid shows the ratio (side chain modification rate, mol%) with respect to the amount of epoxy groups which the polymer (ESSQ-1) has.

4. Synthesis of styrene-maleimide-based copolymer

[Synthesis Example 11]

In a 100 mL two-neck flask under nitrogen, as a polymerization monomer, 10 mol parts of compound (M-1), 10 mol parts of 4-hydroxystyrene, 35 mol parts of methacrylic acid, and 45 mol parts of glycidyl methacrylate, as a radical polymerization initiator 2 mol parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 50 ml of tetrahydrofuran as a solvent were added, and polymerization was carried out at 70°C for 5 hours. After re-precipitation in methanol, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain a styrene-maleimide-based copolymer (this is referred to as a polymer (PM-1)). The weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 30000, and molecular weight distribution (Mw/Mn) was 2.7.

<Preparation and evaluation of liquid crystal aligning agent>

[Example 1: PSA type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent (AL-1)

A solution containing 10 parts by mass of the polymer (PS-1) obtained in Synthesis Example 9 to a solution containing 90 parts by mass of the polymer (P-1) obtained in Synthesis Example 1, 5 parts by mass of the compound (B-1), and the compound (C) -1) 10 mass parts and NMP and butyl cellosolve (BC) were added as a solvent, and a solvent composition made NMP/BC=50/50 (mass ratio) and solid content concentration into the solution of 4.0 mass %. A liquid crystal aligning agent (AL-1) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

(2) Preparation of liquid crystal composition

With respect to 10 g of nematic liquid crystal (Merck Corporation make, MLC-6608), 0.3 mass of the photopolymerizable compound represented by 5 mass % of the liquid crystalline compound represented by a following formula (L1-1) and a following formula (L2-1) % was added and mixed to obtain liquid crystal composition LC1.

(3) Manufacture of PSA type liquid crystal display element

The liquid crystal aligning agent (AL-1) prepared above was applied to each electrode surface of two glass substrates each having a conductive film made of an ITO electrode patterned in a slit shape, on a liquid crystal aligning film printing machine (manufactured by Nippon Shashin Insatsu Co., Ltd.) was applied and heated (pre-baked) for 2 minutes on a hot plate at 80 ° C to remove the solvent, and then heated (post-baked) for 10 minutes on a hot plate at 230 ° C. to form a coating film with an average film thickness of 0.06 µm. . About these coating films, after performing ultrasonic cleaning for 1 minute in ultrapure water, a pair (two sheets) of board|substrates which have a liquid crystal aligning film were obtained by drying in 100 degreeC clean oven for 10 minutes. In addition, the pattern of the electrode used is a pattern similar to the electrode pattern in PSA mode.

Next, an epoxy resin adhesive having an aluminum oxide sphere having a diameter of 5.5 µm is applied to the outer edge of the surface having a liquid crystal aligning film of one of the pair of substrates, and then the liquid crystal aligning film surfaces are overlapped and pressed together so that the surfaces face each other, and the adhesive hardened Next, between a pair of board|substrates at the liquid crystal injection port, after filling the liquid crystal composition LC1 prepared above, the liquid crystal cell was manufactured by sealing the liquid crystal injection port with an acrylic photocuring adhesive agent. After that, by applying an alternating current of 10V with a frequency of 60 Hz between the conductive films of the liquid crystal cell, in the state that the liquid crystal is driving, using an ultraviolet irradiation device using a metal halide lamp as a light source, ultraviolet rays at an irradiation amount of 100,000J/m2 investigated. In addition, this irradiation amount is the value measured using the photometer measured with wavelength 365nm reference|standard. Then, by bonding a polarizing plate to the outer both surfaces of a board|substrate so that the polarization direction may mutually be orthogonal and the projection direction of the optical axis of the ultraviolet-ray of a liquid crystal aligning film to the board|substrate surface and a 45 degree angle may be formed, PSA type liquid crystal display element was manufactured

(4) Evaluation of liquid crystal orientation

About the PSA type liquid crystal display element manufactured above, the presence or absence of the abnormal domain in the change of the contrast when the voltage of 5 V is ON/OFF (applied/released) was observed with an optical microscope, and liquid crystal alignment property evaluated. In evaluation, the case where there was no abnormal domain was "A", the case where there was an abnormal domain in part was made into "B", and the case where there was an abnormal domain as a whole was set as "C". As a result, in this Example, the liquid-crystal orientation was evaluation of "A".

(5) Evaluation of electrical characteristics by voltage retention ratio (VHR)

About the PSA type liquid crystal display element manufactured above, after applying the voltage of 5V with the application time of 60 microseconds, and the span of 167 milliseconds, the voltage retention rate 167 milliseconds after application release was measured. A VHR-1 manufactured by Toyo Technica Co., Ltd. was used as the measuring device. At this time, "S" when the voltage retention ratio is 98% or more, "A" when it is 95% or more and less than 98%, "B" when it is 80% or more and less than 95%, and "C" when it is 50% or more and less than 80%. , was referred to as "D" in the case of less than 50%. As a result, in this Example, the electrical characteristic was evaluation of "S".

(6) Evaluation of film adhesion

After apply|coating a liquid crystal aligning agent (AL-1) using a spinner on a glass substrate and prebaking for 2 minutes on 80 degreeC hotplate, it is 30 in 230 degreeC oven which replaced the inside with nitrogen. By minute heating (post-baking), a coating film having an average film thickness of 0.10 µm was formed. By repeating operation similar to this, two glass substrates with a coating film were produced. On the coating film of one glass substrate in which the coating film was formed, ODF sealing compound (made by Sekisui Chemical Co., Ltd., S-WB42) was apply|coated so that the width might be set to 1 mm, and the coating film of the other glass substrate and ODF sealing compound were applied. joined to make contact. Then, after irradiating the light of 30,000 J/m<2> (365 nm conversion) using a metal halide lamp, it heated in 120 degreeC oven for 1 hour. Then, the adhesiveness of the film|membrane with respect to a board|substrate was evaluated by measuring the adhesive force using Imada Seisakusho's tensile compression tester (model number: SDWS-0201-100SL). Evaluation is "Good (S)" when the adhesion is 175N/cm2 or more, "Good (A)" when it is 150N/cm2 or more and less than 175N/cm2, "Possible (B)" when 125N/cm2 or more and less than 150N/cm2 ", the case of less than 125 N/cm<2> was called "defect (C)". As a result, in this Example, the adhesive force was 173 N/cm<2>, and it was evaluation of adhesiveness "good|favorableness (A)."

(7) Evaluation of storage stability

The change of the viscosity at the time of storing a liquid crystal aligning agent (AL-1) for 23 degreeC and 7 days was measured and compared with the E-type viscometer in 25 degreeC. Evaluation is “good (S)” when the viscosity change is within ±1%, “good (A)” when within ±3%, “possible (B)” when within ±5%, ±5 The case where it was larger than % was called "defect (C)". As a result, in this Example, the viscosity change was +2.5%, and storage stability was evaluated as "good (A)".

(8) Evaluation of reworkability

On a transparent conductive film made of an ITO film formed on one side of a glass substrate having a thickness of 1 mm, a liquid crystal aligning agent (AL-1) is applied with a spinner, and prebaked at 100° C. for 90 seconds on a hot plate, , a coating film having a film thickness of about 0.10 µm was formed. This operation was repeated, and two board|substrates with a coating film were created. Next, the obtained two board|substrates were stored in the dark room of 25 degreeC under nitrogen atmosphere. After 12 hours and 48 hours from the start of storage, the substrates are taken out one by one, immersed in a beaker with NMP temperature controlled at 40° C. for 2 minutes, washed several times with ultrapure water, and water droplets on the surface are blown with air. has been removed About this board|substrate, the peelability (rework property) from the board|substrate of a liquid crystal aligning film was evaluated by observing with the optical microscope and examining the presence or absence of the residue of a coating film. The evaluation was evaluated as "Excellent (S)" when the residue of the coating film was not completely observed after NMP immersion even in the substrate taken out after 48 hours from the start of storage, and the residue of the coating film was observed on the substrate after 48 hours, but after 12 hours “Good (A)” indicates that no residue of the coating film is completely observed on the substrate, “Possible (B)” indicates that a microscopic residue is observed on the substrate after 12 hours, and residue of the coating film on the substrate after 12 hours A case where was observed was called "defective (C)". As a result, in this Example, the rework property was evaluation of "excellent (S)".

[Examples 2 to 4 and Comparative Examples 1 and 2]

Liquid crystal aligning agents (AL-2) to (AL-4), (AR-1), (AR-2) in the same solvent composition and solid content concentration as in Example 1 except for changing the compounding composition as shown in Table 3 was prepared Moreover, while carrying out similarly to Example 1 using each liquid crystal aligning agent, and evaluating storage stability, the adhesiveness of a film|membrane, and rework property, the PSA type liquid crystal display element was manufactured and liquid-crystal orientation and voltage retention were evaluated. Table 3 shows the evaluation results. In addition, in Table 3, "-" shows that the compound is not used.

[Example 5: Optical vertical liquid crystal display device]

(1) Preparation of liquid crystal aligning agent, and evaluation of storage stability, the adhesiveness of a film|membrane, and rework property

A liquid crystal aligning agent (AL-5) was prepared with the solvent composition and solid content concentration similar to Example 1 except the point which changed the compounding composition as shown in Table 3. Moreover, it carried out similarly to Example 1 using liquid crystal aligning agent (AL-5), and evaluated storage stability, the adhesiveness of a film|membrane, and rework property. Table 3 shows the evaluation results.

(2) Manufacture of an optical vertical liquid crystal display device

On the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, the liquid crystal aligning agent (AL-5) prepared above was apply|coated using the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, the surface of the coating film was irradiated with 1,000 J/m of polarized ultraviolet light containing a bright line of 313 nm using an Hg-Xe lamp and a Gran Taylor prism from a direction inclined by 40° from the substrate normal to impart liquid crystal alignment ability. . The same operation was repeated and a pair (two sheets) of board|substrates which have a liquid crystal aligning film were created.

After applying by screen printing an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 µm to the outer periphery of the surface having one liquid crystal aligning film in the substrate, the liquid crystal aligning film surfaces of a pair of substrates are opposed to each other, and each substrate was pressed so that the projection direction of the optical axis of the ultraviolet rays to the substrate surface was antiparallel, and the adhesive was thermosetted at 150°C for 1 hour. Next, after filling the gap between the substrates at the liquid crystal injection port with negative liquid crystal (Merck Corporation, MLC-6608), the liquid crystal injection port was sealed with an epoxy adhesive. Moreover, in order to eliminate the flow orientation at the time of liquid crystal injection, after heating this at 130 degreeC, it cooled slowly to room temperature. Next, by bonding a polarizing plate to the outer both surfaces of the substrate so that the polarization direction thereof is orthogonal to each other, and forms an angle of 45° with the projection direction of the optical axis of the ultraviolet ray of the liquid crystal aligning film to the substrate surface, an optical vertical type liquid crystal display element was manufactured

(3) Evaluation of liquid crystal orientation

About the optical vertical type liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, the liquid-crystal orientation was evaluation of "A".

(4) Evaluation of electrical characteristics by voltage retention ratio (VHR)

About the optical vertical type liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the electrical characteristic. As a result, in this Example, the electrical characteristic was evaluated as "A".

[Comparative Example 3]

A liquid crystal aligning agent (AR-3) was prepared with the solvent composition and solid content concentration similar to Example 1 except the point which changed the compounding composition as shown in Table 3. Moreover, while carrying out similarly to Example 1 using liquid crystal aligning agent (AR-3), and evaluating storage stability, adhesiveness of a film|membrane, and rework property, an optical vertical type liquid crystal display element was manufactured, and liquid-crystal orientation and voltage retention of evaluation was performed. Table 3 shows the evaluation results.

[Example 6: Vertical liquid crystal display device]

(1) Preparation of liquid crystal aligning agent, and evaluation of storage stability, the adhesiveness of a film|membrane, and rework property

A liquid crystal aligning agent (AL-6) was prepared with the solvent composition and solid content concentration similar to Example 1 except the point which changed the compounding composition as shown in Table 3. Moreover, it carried out similarly to Example 1 using liquid crystal aligning agent (AL-6), and evaluated storage stability, the adhesiveness of a film|membrane, and rework property. Table 3 shows the evaluation results.

(2) Manufacturing of vertical liquid crystal display device

On the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, the liquid crystal aligning agent (AL-6) prepared above was apply|coated using the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. By repeating this operation, a pair (two sheets) of the board|substrate which has a liquid crystal aligning film was created.

On the outer periphery of the surface having one liquid crystal aligning film of the substrate, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 μm is applied by screen printing, and then overlapped so that each liquid crystal aligning film surface is facing each other and pressed, the adhesive hardened Next, in the liquid crystal injection port, after filling the negative liquid crystal (MLC-6608, manufactured by Merck) between a pair of substrates, sealing the liquid crystal injection port with an acrylic light-curing adhesive, and bonding a polarizing plate to both sides of the outer side of the substrate A liquid crystal display element was manufactured.

(3) Evaluation of liquid crystal orientation

About the vertical liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, the liquid-crystal orientation was evaluation of "A".

(4) Evaluation of electrical characteristics by voltage retention ratio (VHR)

About the vertical liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the electrical characteristic. As a result, in this Example, the electrical characteristic was evaluated as "A".

[Example 7: FFS type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent, and evaluation of storage stability, the adhesiveness of a film|membrane, and rework property

Except for having changed the compounding composition as shown in Table 3, the liquid crystal aligning agent (AL-7) was prepared with the solvent composition and solid content concentration similar to Example 1. Moreover, it carried out similarly to Example 1 using liquid crystal aligning agent (AL-7), and evaluated storage stability, the adhesiveness of a film|membrane, and rework property. Table 3 shows the evaluation results.

(2) Manufacturing of FFS type liquid crystal display element

A glass substrate having a flat electrode (bottom electrode), an insulating layer, and a comb-toothed electrode (top electrode) laminated on one side in this order (referred to as a first substrate), and a glass substrate without an electrode (as a second substrate) ) was prepared. Next, the liquid crystal aligning agent (AL-7) was apply|coated with the spinner to each of the single side|surface of the electrode formation surface of a 1st board|substrate and a 2nd board|substrate, and it heated (prebaked) for 3 minutes on a 110 degreeC hotplate. Then, drying (post-baking) was performed for 30 minutes in the 230 degreeC oven which substituted the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.08 micrometer was formed. Next, the coating film surface was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 1000 rpm, a stage movement speed of 3 cm/sec, and a bushy foot press-in length of 0.3 mm. Then, a pair of board|substrates which have a liquid crystal aligning film were obtained by performing ultrasonic cleaning for 1 minute in ultrapure water, and drying for 10 minutes in 100 degreeC clean oven then.

Next, with respect to a pair of board|substrates which have a liquid crystal aligning film, the epoxy resin adhesive which left the liquid crystal injection hole in the edge of the surface on which the liquid crystal aligning film was formed, and put the aluminum oxide sphere of diameter 3.5 micrometers was screen-printed and apply|coated. Then, the board|substrates were superimposed on each other and pressed, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, in the liquid crystal injection port, after filling the gap between a pair of board|substrates with negative liquid crystal (Merck Corporation make, MLC-6608), the liquid crystal injection port was sealed with the epoxy adhesive. Furthermore, in order to eliminate the flow orientation at the time of liquid crystal injection, after heating this at 120 degreeC, it cooled slowly to room temperature, and the liquid crystal cell was manufactured. In addition, when a pair of board|substrates were overlapped with each other, it was made so that the rubbing method of each board|substrate was antiparallel. Next, the polarizing plate was bonded to the outer both surfaces of the board|substrate in a liquid crystal cell, and the FFS-type liquid crystal display element was obtained.

(3) Evaluation of liquid crystal orientation

About the FFS-type liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, the liquid-crystal orientation was evaluation of "A".

(4) Evaluation of electrical characteristics by voltage retention ratio (VHR)

About the FFS-type liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the electrical characteristic. As a result, in this Example, the electrical characteristic was evaluated as "A".

[Examples 8, 9 and Comparative Examples 4,5]

Liquid crystal aligning agents (AL-8), (AL-9), (AR-4), (AR-5) with the same solvent composition and solid content concentration as Example 1 except for changing the compounding composition as shown in Table 3 were prepared respectively. Moreover, while carrying out similarly to Example 1 using each liquid crystal aligning agent, and evaluating storage stability, the adhesiveness of a film|membrane, and rework property, the FFS-type liquid crystal display element was manufactured and liquid-crystal orientation and voltage retention were evaluated. Table 3 shows the evaluation results.

[Example 10: Optical FFS type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent, and evaluation of storage stability, the adhesiveness of a film|membrane, and rework property

Except for having changed the compounding composition as shown in Table 3, the liquid crystal aligning agent (AL-10) was prepared with the solvent composition and solid content concentration similar to Example 1. Moreover, it carried out similarly to Example 1 using liquid crystal aligning agent (AL-10), and evaluated storage stability, the adhesiveness of a film|membrane, and rework property. Table 3 shows the evaluation results.

(2) Manufacture of optical FFS type liquid crystal display element

The 1st board|substrate and 2nd board|substrate similar to Example 7 were prepared. Next, a liquid crystal aligning agent (AL-10) is apply|coated with a spinner to each of the one board|substrate surface of the electrode formation surface of a 1st board|substrate and a 2nd board|substrate, and it heats for 1 minute on an 80 degreeC hotplate (prebaking). did. Then, drying (post-baking) was performed for 30 minutes in 230 degreeC oven which substituted the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.1 micrometer was formed. The obtained coating film was subjected to photo-alignment treatment by irradiating 1,000 J/m 2 of ultraviolet rays containing a linearly polarized 254 nm bright line from the normal line direction to the substrate using a Hg-Xe lamp. In addition, this irradiation amount is the value measured using the photometer measured with wavelength 254nm reference|standard. Next, the coating film to which the photo-alignment process was given was heated in a 230 degreeC clean oven for 30 minutes, heat processing was performed, and the liquid crystal aligning film was formed.

Next, about one board|substrate among a pair of board|substrates in which the liquid crystal aligning film was formed, the epoxy resin adhesive agent which put the aluminum oxide sphere of 3.5 micrometers in diameter in the outer edge of the surface which has a liquid crystal aligning film was apply|coated by screen printing. Then, the board|substrates were superimposed and pressed together so that the projection direction of the polarization axis|shaft to the board|substrate surface at the time of light irradiation became antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, after filling a negative liquid crystal (Merck Corporation make, MLC-6608) between a pair of board|substrates at the liquid crystal injection port, the liquid crystal injection port was sealed with the epoxy adhesive, and the liquid crystal cell was obtained. Furthermore, in order to eliminate the flow orientation at the time of liquid crystal injection, after heating this at 120 degreeC, it cooled slowly to room temperature. Then, the polarizing plate was bonded together on the outer both surfaces of the board|substrate in a liquid crystal cell, and the liquid crystal display element was obtained. In addition, by carrying out the above series of operations by changing the ultraviolet irradiation amount after post-baking in the range of 100 to 10,000 J/m 2 , three or more liquid crystal display elements with different ultraviolet irradiation amounts were manufactured, and the best alignment characteristics were obtained. The liquid crystal display element of the exposure amount (optimum exposure amount) was used for the following evaluation.

(3) Evaluation of liquid crystal orientation

About the optical FFS type liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the liquid-crystal orientation. As a result, in this Example, the liquid-crystal orientation was evaluation of "A".

(4) Evaluation of electrical characteristics by voltage retention ratio (VHR)

About the optical FFS type|mold liquid crystal display element manufactured above, it carried out similarly to the said Example 1, and evaluated the electrical characteristic. As a result, in this Example, the electrical characteristic was evaluated as "A".

As shown in Table 3, Examples 1 to 10 in which Compound [B] and Compound [C] were used together as a crosslinking agent were evaluation of A or B for liquid crystal orientation, and S for electrical properties, film adhesion and storage stability , A or B. Moreover, about rework property, it was excellent in S or A. On the other hand, in the comparative example 1 using only compound [B] as a crosslinking agent, storage stability and rework property were evaluation of C. In addition, in the comparative example 5 using only compound [C] as a crosslinking agent, liquid-crystal orientation and rework property were evaluation of C. As a crosslinking agent, the storage stability of Comparative Example 3 in which the compound [B] and another crosslinking agent were combined, and Comparative Examples 2 and 4 in which the compound [C] and another crosslinking agent were combined were evaluation of C in all.

[Example 11]

A liquid crystal aligning agent (AL-11) was prepared with the solvent composition and solid content concentration similar to Example 1 except the point which changed the compounding composition as shown in Table 4. Moreover, while carrying out similarly to Example 1 using a liquid crystal aligning agent (AL-11), and evaluating storage stability, adhesiveness of a film|membrane, and rework property, a PSA type liquid crystal display element is manufactured and liquid-crystal orientation and voltage retention are evaluated did The evaluation results are shown in Table 4 together with the results of Comparative Example 1.

[Example 12]

Except for having changed the compounding composition as shown in Table 4, the liquid crystal aligning agent (AL-12) was prepared with the solvent composition and solid content concentration similar to Example 1. Moreover, while carrying out similarly to Example 1 using a liquid crystal aligning agent (AL-12), and evaluating storage stability, the adhesiveness of a film|membrane, and rework property, it carried out similarly to Example 7, and produced an FFS-type liquid crystal display element, and liquid crystal The orientation and voltage retention were evaluated. The evaluation results are shown in Table 4 together with the results of Comparative Example 4.

As shown in Table 4, Examples 11 and 12 in which Compound [B] and Compound [C] were used in combination as a crosslinking agent were evaluated as S or A for liquid crystal orientation, electrical properties, film adhesion, storage stability and reworkability. . For these results, when compared with the comparative examples (Comparative Example 1 and Comparative Example 4) with the same driving mode, respectively, storage stability and reworkability were particularly improved in Example 11, and storage stability was particularly improved in Example 12, there was.

From the above results, the liquid crystal aligning agent containing the compound [B] and the compound [C] as a crosslinking agent together with the polymer component is excellent in storage stability and can form a liquid crystal aligning film having good rework property, liquid crystal alignment property and electrical properties. It became clear what could be Moreover, the adhesiveness with a board|substrate was also sufficiently high as for the alignment film formed with the said liquid crystal aligning agent.

Claims (14)

The liquid crystal aligning agent containing following (A) component, (B) component, and (C)component.
(A) polymer
(B) having two or more nucleophilic functional groups or acidic functional groups in one molecule, and at least one of the nucleophilic functional groups or acidic functional groups present in one molecule, nitrogen atom, sulfur atom or oxygen atom , a compound having a partial structure [T] to which a leaving group that is detached by at least one of heat and light is bonded (with the exception of component (A) above)
(C) a compound having two or more spherical functional groups in one molecule (except for the component (A) and the compound having a radically polymerizable carbon-carbon double bond) According to claim 1,
The component (B) is a compound having two or more nucleophilic functional groups in one molecule, and at least one of the nucleophilic functional groups present in one molecule has the partial structure [T],
The electrophilic functional group of the component (C) is selected from the group consisting of an isocyanate group, a protected isocyanate group, a cyclic carbonate group, a methylol group, a protected methylol group, a group having a ketene structure, and a group having a Meldrum acid structure The liquid crystal aligning agent which is at least 1 sort(s) used. 3. The method of claim 2,
The liquid crystal aligning agent whose said (B) component is a compound represented by following formula (1).

(In formula (1), X ¹ is a nitrogen atom, a sulfur atom, an oxygen atom, or a group represented by the following formula (x-1); Y ¹ is a leaving group which is released by at least one of heat and light; R ¹ is a hydrogen atom or a monovalent organic group; R ² is a k-valent organic group; k is an integer greater than or equal to 2; when X ¹ is a sulfur atom or an oxygen atom, m is 1 and n is 0 , and when X ¹ is a nitrogen atom or a group represented by the following formula (x-1), m is 1 or 2, and n is 2-m; a plurality of X ^1s in the formula are the same or different from each other; In the case where a plurality of Y ^1s exist, a plurality of Y ^1s are the same or different from each other)

(In formula (x-1), R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms; “*” represents a bond; “*1” represents a bond with R ² ) 4. The method of claim 3,
Said ^R2 is k-valent group which does not have an aromatic ring, The liquid crystal aligning agent. 4. The method of claim 3,
R ² is a chain hydrocarbon group having a k valence, or between carbon-carbon bonds of the chain hydrocarbon group -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ - , -NR ⁴ -CO-O-, -NR ⁴ -CO-NR ⁵ -, -CO-NR ⁴ -NR ⁵ - or a k-valent group including a non-aromatic heterocycle (provided that R ⁴ and R ⁵ is a hydrogen atom or a C1-C10 monovalent organic group each independently), The liquid crystal aligning agent. According to claim 1,
The component (B) is a compound having two or more acidic functional groups in one molecule, and at least one of the acidic functional groups present in one molecule having the partial structure [T],
The electrophilic functional group which the said (C) component has is at least 1 sort(s) selected from the group which consists of a cyclic ether group, a cyclic carbonate group, an oxazoline group, and group which has (beta)-hydroxyamide structure, The liquid crystal aligning agent. 7. The method of claim 6,
The liquid crystal aligning agent whose said (B) component is a compound represented by following formula (3).

(in formula (3), X ² is a carboxylic acid group, a phosphoric acid group, a phosphorous acid group, or a sulfonic acid group; X ³ is a protected carboxylic acid group, a protected phosphoric acid group, a protected phosphorous acid group, or a protected sulfonic acid group) R ⁶ is an organic group having a valence of (i+j); i is an integer of 0 or more; j is an integer of 1 or more; provided that (i+j)≥2 is satisfied; when i is 2 or more, a plurality of Xs ² is the same as or different from each other; when j is 2 or more, a plurality of X ³ are the same or different from each other) 8. The method of claim 7,
R ⁶ is a chain hydrocarbon group having a valence of (i+j), or between carbon-carbon bonds of the chain hydrocarbon group -O-, -S-, -CO-, -COO-, -NR ⁷ -, -CO-NR ⁷ - , -NR ⁷ -CO-O-, -NR ⁷ -CO-NR ⁸ -, -CO-NR ⁷ -NR ⁸ - or a (i+j) valent group containing a non-aromatic heterocycle (provided that R ⁷ and R ⁸ ) The liquid crystal aligning agent which is each independently a hydrogen atom or a C1-C10 monovalent organic group) or (i+j) valence alicyclic hydrocarbon group. 7. The method of claim 6,
The liquid crystal aligning agent in which said (C)component does not have an aromatic ring. 10. The method according to any one of claims 1 to 9,
The component (A) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and a polymer having a structural unit derived from a monomer having a carbon-carbon unsaturated bond. Liquid crystal aligning agent. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-9. The manufacturing method of the liquid crystal aligning film which apply|coats the liquid crystal aligning agent in any one of Claims 1-9 on a board|substrate, and after apply|coating the said apply|coating, light-irradiates and provides liquid-crystal aligning ability. A liquid crystal element provided with the liquid crystal aligning film of Claim 11. The process of apply|coating the liquid crystal aligning agent in any one of Claims 1-9 on each said electrically conductive film of a pair of board|substrates which have an electrically conductive film, and forming a coating film;
A step of constructing a liquid crystal cell by arranging a pair of substrates coated with the liquid crystal aligning agent so that the coating film faces each other with a liquid crystal layer interposed therebetween;
A process of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films
A method of manufacturing a liquid crystal device comprising a.