KR102454059B1 - Liquid crystal aligning agent - Google Patents

Abstract

(R⁴는 수소 원자 또는 탄소수 1∼6의 알킬기, R⁵는 수소 원자 또는 탄소수 1∼6의 알킬기, R⁶은 탄소수 2∼4의 알칸디일기, R⁷∼R¹⁰은 각각 독립적으로 수소 원자 또는 1가의 유기기이고;
R¹¹∼R¹³은 각각 독립적으로 수소 원자 또는 탄소수 1∼3의 알킬기임).(Project) It is hard to swell a printing plate, and the liquid crystal aligning agent with favorable printability is provided.
(Solution) A polymer component, a solvent having a phosphorus atom, N,N-dimethylpropyleneurea, tetrahydro-4H-pyran-4-one, tetramethylenesulfoxide, 3-methylcyclohexanone, 4-methylcyclohexane On, a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and at least one specific solvent selected from the group consisting of a compound represented by the following formula (10) It is contained in a liquid crystal aligning agent:

(R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁶ is an alkanediyl group having 2 to 4 carbon atoms, R ⁷ to R ¹⁰ are each independently a hydrogen atom or a monovalent organic group;
R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

Description

Liquid crystal aligning agent {LIQUID CRYSTAL ALIGNING AGENT}

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element.

Conventionally, as a liquid crystal element, various types of driving systems have been developed, which differ in electrode structure and physical properties of liquid crystal molecules to be used, for example, TN type, STN type, VA type, and in-plane switching type (IPS type). , FFS type, and various liquid crystal devices such as optical compensation vent type (OCB type) are known. These liquid crystal elements have a liquid crystal aligning film for orientating a liquid crystal molecule. As a material of a liquid crystal aligning film, since various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable, polyamic acid, a polyimide, etc. are used.

A liquid crystal aligning agent WHEREIN: A polymer component is melt|dissolving in the solvent, A liquid crystal aligning film is formed by apply|coating and heating a liquid crystal aligning agent to a board|substrate. Here, as a solvent for a liquid crystal aligning agent, the organic solvent with high polymer solubility, for example, aprotic polar solvents, such as N-methyl- 2-pyrrolidone and (gamma)-butyrolactone, is generally used. Moreover, in order to make the applicability|paintability (printability) of the liquid crystal aligning agent good at the time of apply|coating a liquid crystal aligning agent to a board|substrate, surface tension is comparatively similar with an aprotic polar solvent, for example, butyl cellosolve etc. A low organic solvent is used together (for example, refer patent document 1 and patent document 2).

As a method of apply|coating a liquid crystal aligning agent to a board|substrate, various methods, such as the spin coating method, the offset printing method, the inkjet method, are applied. For example, the offset printing method is generally performed using a transfer printing apparatus in which a liquid crystal aligning agent is applied to a printing plate made of a resin such as APR (registered trademark), and the liquid crystal aligning agent is transferred onto a substrate by the printing plate ( For example, refer to patent document 3).

Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Laid-Open Patent Publication No. 2010-156934 Japanese Laid-Open Patent Publication No. 2001-343649

The butyl cellosolve generally used for the purpose of the improvement of the applicability|paintability of a liquid crystal aligning agent exists in the tendency for APR resin to swell easily. Therefore, when apply|coating the liquid crystal aligning agent containing a butyl cellosolve to a board|substrate by offset printing, when application|coating to a printing plate is performed repeatedly, we are anxious that a printing plate swells and printability falls. Moreover, as a solvent component of a liquid crystal aligning agent, even when printing is performed continuously, it is difficult for a polymer to precipitate on a printing machine, and it is calculated|required that printability (continuous printability) is favorable.

This invention was made in view of the said subject, It is hard to swell a printing plate, and it makes it one objective to provide the liquid crystal aligning agent with favorable printability.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by using a specific organic solvent as a solvent, as a result of earnestly examining in order to achieve the subject of the above prior art, and came to complete this invention. Specifically, the following liquid crystal aligning agents, a liquid crystal aligning film, and a liquid crystal element are provided by this invention.

In one aspect, the present invention provides a polymer component, a solvent having a phosphorus atom, N,N-dimethylpropyleneurea, tetrahydro-4H-pyran-4-one, tetramethylenesulfoxide, 3-methylcyclohexanone, At least selected from the group consisting of 4-methylcyclohexanone, a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (10) A liquid crystal aligning agent containing one specific solvent is provided:

(In formula (1), R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

In formula (2), R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁶ is an alkanediyl group having 2 to 4 carbon atoms;

In formula (3), R ⁷ to R ¹⁰ are each independently a hydrogen atom or a monovalent organic group;

In formula (10), R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

By using said specific solvent as a solvent component of a liquid crystal aligning agent, the liquid crystal aligning agent with which a printing plate does not swell easily can be obtained. Moreover, even when printing is performed continuously, a polymer is hard to precipitate on a printing machine, and printability can be made favorable.

In another aspect, the present invention provides a liquid crystal aligning film formed by the liquid crystal aligning agent. In addition, in another aspect, there is provided a liquid crystal element having a liquid crystal aligning film formed by the liquid crystal aligning agent.

Since the liquid crystal aligning film of this invention is formed using the liquid crystal aligning agent containing the said specific solvent, while being able to form a uniform coating film, film quality is favorable. In addition, when a liquid crystal element is manufactured using the liquid crystal aligning agent, printing defects can be reduced in a manufacturing process, and consequently, the yield of a product can be improved.

(Form for implementing the invention)

Below, each component contained in the liquid crystal aligning agent of this invention, and the other component mix|blended arbitrarily as needed are demonstrated.

<Polymer component>

The liquid crystal aligning agent of this invention contains a polymer component. The main skeleton of the polymer is not particularly limited, and for example, polyamic acid, polyamic acid ester, polyimide, polysiloxane, polyester, polyamide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polystyrene derivative , poly(styrene-phenylmaleimide) derivatives, and main skeletons such as poly(meth)acrylate. In addition, (meth)acrylate means containing an acrylate and a methacrylate.

It is preferable that the polymer component of a liquid crystal aligning agent is at least 1 sort(s) chosen from the group which consists of a polyamic acid, polyamic acid ester, a polyimide, and polyorganosiloxane among the above from the point with the high printability improvement effect by a specific solvent. In addition, at the time of preparation of a liquid crystal aligning agent, as a polymer, you may use individually by 1 type, and may use it in combination of 2 or more type.

[Polyamic acid]

The polyamic acid in this invention can be obtained by making tetracarboxylic dianhydride and diamine react, for example.

(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 of these include aliphatic tetracarboxylic dianhydride, such as 1,2,3,4-butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride; 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-fura nyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran- 2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6- Tricarboxy-2-carboxymethylnorbornane-2:3,5:6-2 anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride, etc.;

As aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride etc.;

In addition to those mentioned respectively, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesis, the above properties can be improved, the solubility of the polymer in a solvent containing a specific solvent can be made higher, and the effect of improving printability can be made higher From this point, it is preferable to contain alicyclic tetracarboxylic dianhydride. In addition, among the alicyclic tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane- It is preferable to contain at least 1 sort(s) selected from the group which consists of 2:4,6:8-2 anhydride and 1,2,3,4- cyclobutanetetracarboxylic dianhydride, and 2,3,5-tri Carboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2anhydride and 1,2,3,4-cyclobutanetetracarbon It is especially preferable that at least 1 sort(s) selected from the group which consists of an acid dianhydride is included.

As tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2anhydride And when at least 1 sort(s) selected from the group which consists of 1,2,3,4-cyclobutanetetracarboxylic dianhydride is included, content of the sum total of these compounds is tetracarboxylic acid 2 used for the synthesis|combination of polyamic acid. It is preferable that it is 10 mol% or more with respect to the whole amount of anhydride, and it is more preferable that it is 20-100 mol%.

(diamine)

As diamine used for the synthesis|combination of polyamic acid, an aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane etc. are mentioned, for example. Specific examples of these diamines include, as aliphatic diamines, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, and the like. ;

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and the like;

As the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'- (p-phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 2,6-diaminopyridine, 3,6-diaminocarbazole, N,N'-bis( 4-Aminophenyl)-benzidine, 1,4-bis(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene -5-Amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy- 3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-dia cholestenyl minobenzoate, 3,5-diaminobenzoic acid lanostanyl, 3,6-bis(4-aminobenzoyloxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3, 5-Diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4 -(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, N-[4-(2-aminoethyl)phenyl]benzene-1,4 -diamine, N-[4-(aminomethyl)phenyl]benzene-1,4-diamine, diamine containing cinnamic acid structure and the following formula (D-1)

(In formula (D-1), X ^I and X ^II are each independently a single bond, -O-, *-COO-, *-OCO-, or *-NH-CO- (provided that "*" the attached bond is bonded to a diaminophenyl group), R ^I and R ^II are each independently an alkanediyl having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2; c is an integer from 1 to 20, n is 0 or 1, m is 0 or 1, provided that a and b are not simultaneously 0, and when X ^I is *-NH-CO-, n is 0)

compounds represented by ;

As the diaminoorganosiloxane, for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane etc. are mentioned, respectively, and the diamine of Unexamined-Japanese-Patent No. 2010-97188 is used. can In addition, these diamines can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the compound represented by the formula (D-1) include compounds represented by each of the following formulas (D-1-1) to (D-1-4).

It is preferable that the diamine used for the synthesis|combination of a polyamic acid contains 30 mol% or more of aromatic diamine with respect to all diamine, It is more preferable to contain 50 mol% or more, It is especially preferable to contain 80 mol% or more.

(Synthesis of polyamic acid)

A polyamic acid can be obtained by making the above tetracarboxylic dianhydride and diamine react with a molecular weight modifier as needed. The ratio of using tetracarboxylic dianhydride and diamine to be used in the synthesis reaction of polyamic acid is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine. As a molecular weight modifier, For example, Acid monoanhydrides, such as maleic anhydride, phthalic anhydride, itaconic anhydride, Monoamine compounds, such as aniline, cyclohexylamine, n-butylamine, Monoisocyanate compounds, such as phenyl isocyanate and naphthyl isocyanate and the like. It is preferable that the usage ratio of a molecular weight modifier sets it as 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine 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, tetramethylurea, hexamethylphosphor. At least one selected from the group consisting of triamide, m-cresol, xylenol, halogenated phenol and specific solvents shown below is used as a solvent, or at least one of these and other organic solvents (eg, butyl cell Rosolv, diethylene glycol diethyl ether, etc.) is preferably used. It is preferable that the amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50 wt% with respect to the total amount (a+b) of the 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.

[Polyimide]

The polyimide in the present invention can be obtained 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 precursor thereof are cyclized by dehydration, or a partial imidized product in which only a part of the amic acid structure is dehydrated and cyclized to coexist with a amic acid structure and an imide ring structure. good night. It is preferable that the imidation ratio of the polyimide in this invention is 30 % or more, It is more preferable that it is 40 to 99 %, It is more preferable that it is 50 to 99 %. This imidation ratio shows the ratio which the number of imide ring structures occupies with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures, as a percentage. Here, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of the polyamic acid is preferably performed by heating the polyamic acid or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating as necessary. . Among these, the latter method is preferable.

In the method of adding a dehydrating agent and a dehydration ring closure catalyst to a solution of polyamic acid, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. 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. It is preferable that the usage-amount of a dehydration ring closure catalyst shall be 0.01-10 mol with respect to 1 mol of the dehydrating agent 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, and the reaction time is preferably 1.0 to 120 hours.

In this way, the reaction solution containing a polyimide is obtained. After this reaction solution may be used for preparation of a liquid crystal aligning agent as it is, after removing a dehydrating agent and a dehydration ring closure catalyst from a reaction solution, you may provide for preparation of a liquid crystal aligning agent, after isolating a polyimide, it uses for preparation of a liquid crystal aligning agent also good These purification operations can be performed according to a known method. In addition, polyimide can also be obtained by imidation of polyamic acid ester.

[Polyamic acid ester]

The polyamic acid ester in the present invention is, for example, [I] a polyamic acid obtained by the above synthesis reaction and an esterifying agent (for example, methanol, ethanol, N,N-dimethylformamide diethyl acetal, etc.) Reaction method, [II] Tetracarboxylic acid diester and diamine are mixed in an organic solvent with a suitable dehydration catalyst (for example, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl) ) A method of reacting in the presence of -4-methylmorpholinium halide, a phosphorus-based condensing agent, etc.), [III] The tetracarboxylic acid diester dihalide and diamine are mixed in an organic solvent with an appropriate base (eg, pyridine, triethylamine, sodium hydroxide, or the like).

The polyamic acid ester made to contain in a liquid crystal aligning agent may have only a amic-acid ester structure, and the partial esterification in which a amic-acid structure and a amic-ester structure coexist may be sufficient as it. Moreover, 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.

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa·s, and a solution viscosity of 15 to 500 mPa·s when this is a solution having a concentration of 10% by weight. It is more preferable to have In addition, the solution viscosity (mPa*s) of the said polymer is 10 weight by weight of the concentration prepared using the positive solvent (for example, gamma -butyrolactone, N-methyl-2-pyrrolidone, etc.) of the said polymer. % of the polymer solution WHEREIN: It is the value measured at 25 degreeC using the E-type rotational viscometer.

It is preferable that the weight average molecular weights of polystyrene conversion measured by gel permeation chromatography (GPC) about the polyamic acid, polyamic acid ester, and polyimide contained in the liquid crystal aligning agent of this invention are 500-100,000, 1,000- It is more preferable that it is 50,000.

[Polyorganosiloxane]

The polyorganosiloxane in the present invention can be obtained, for example, by hydrolyzing or hydrolyzing/condensing a hydrolyzable silane compound, preferably in the presence of a suitable organic solvent, water, and a catalyst.

Examples of the hydrolyzable silane compound used in the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethane. alkoxysilane compounds such as oxysilane, trimethoxysilylpropyl succinic anhydride, dimethyldimethoxysilane and dimethyldiethoxysilane;

3-Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyl nitrogen/sulfur-containing alkoxysilane compounds such as trimethoxysilane, 3-aminopropyltriethoxysilane and N-(3-cyclohexylamino)propyltrimethoxysilane;

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, Epoxy group-containing silane compounds, such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane;

3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, p-styryltri Unsaturated bond containing alkoxysilane compounds, such as methoxysilane, etc. are mentioned. A hydrolysable silane compound can be used individually by 1 type among these or in combination of 2 or more type. In addition, "(meth)acryloxy" is a meaning including "acryloxy" and "methacryloxy."

The hydrolysis/condensation reaction is carried out by reacting one or two or more of the above silane compounds with water, preferably in the presence of a suitable catalyst and an 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 (for example, triethylamine, tetramethylammonium hydroxide, etc.), a titanium compound, a zirconium compound, etc. are mentioned, for example. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set, but for example, preferably 0.01 to 3 moles with respect to the total amount of the silane compound. Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, and alcohols, and among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. Preferably the ratio of the organic solvent used is 50 to 1,000 parts by weight with respect to 100 parts by weight in total of the silane compound used for the reaction.

The hydrolysis/condensation reaction is preferably carried out by heating, for example, in an oil bath or the like. In that case, it is preferable that heating temperature shall be 130 degrees C or less, and it is preferable that heating time shall be 0.5 to 12 hours. After completion of the reaction, polysiloxane can be obtained by removing the solvent from the organic solvent layer separated from the reaction solution.

When applying to the liquid crystal aligning agent for liquid crystal display elements of TN type, STN type, or vertical alignment type, you may introduce|transduce specific groups, such as group which has a liquid-crystal aligning group and a photo-alignment structure, into the side chain of polyorganosiloxane. Although the method of synthesizing the polyorganosiloxane having these specific groups in the side chain is not particularly limited, for example, an epoxy group-containing silane compound or a mixture of an epoxy group-containing silane compound and other silane compounds is hydrolyzed and condensed to have an epoxy group A method of synthesizing polyorganosiloxane and then reacting the obtained epoxy group-containing polyorganosiloxane with the carboxylic acid having the above specific group, etc. are mentioned. The reaction between the epoxy group-containing polyorganosiloxane and carboxylic acid can be carried out according to a known method.

The polyorganosiloxane preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC in the range of 500 to 100,000, more preferably in the range of 1,000 to 30,000, still more preferably 1,000 to 20,000. do. When the weight average molecular weight of polyorganosiloxane exists in the said range, when manufacturing a liquid crystal aligning film, it will be easy to handle, and the obtained liquid crystal aligning film will have sufficient material strength and a characteristic.

The liquid crystal aligning agent of this invention WHEREIN: The content rate (total amount when 2 or more types) of the polymer chosen from the group which consists of a polyamic acid, polyamic acid ester, a polyimide, and polyorganosiloxane is the polymer in a liquid crystal aligning agent. It is preferable that it is 50 weight% or more with respect to the total amount of a component, and it is more preferable that it is 60 weight% or more. Moreover, from a viewpoint of obtaining the effect of this invention more suitably, it is preferable as a polymer component to contain at least 1 sort(s) selected from the group which consists of a polyamic acid, polyamic acid ester, and a polyimide. It is preferable that it is 40 weight% or more with respect to the total amount of the polymer component in a liquid crystal aligning agent, and, as for the content rate of the sum total of the polyamic acid in a liquid crystal aligning agent, polyamic acid ester, and a polyimide, it is more preferable that it is 60 weight% or more.

<solvent>

The liquid crystal aligning agent of this invention is a liquid composition in which a polymer component disperse|distributes or melt|dissolves in a solvent. The said liquid crystal aligning agent is a solvent which has a phosphorus atom as a solvent (henceforth a "phosphorus containing solvent"), N,N-dimethylpropylene urea, tetrahydro-4H-pyran-4-one, tetramethylene sulfoxide, 3-methylcyclohexanone, 4-methylcyclohexanone, the compound represented by the formula (1), the compound represented by the formula (2), the compound represented by the formula (3), and the compound represented by the formula (10) It contains the specific solvent which is at least 1 sort(s) selected from the group which consists of.

[Phosphorus containing solvent]

The phosphorus-containing solvent is not particularly limited as long as it is a compound having at least one phosphorus atom in the molecule, but it is at least one selected from the group consisting of compounds represented by each of the following formulas (p-1) to (p-4). desirable:

(In formulas (p-1) to (p-4), X ¹ and Y ¹ are each independently an oxygen atom or a sulfur atom;

R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent organic group;

provided that R ¹ and R ² may be bonded to each other to form a ring;

R ³ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and two R ³ bonded to a nitrogen atom may be bonded to each other to form a monovalent nitrogen-containing heterocyclic group together with the nitrogen atom;

provided that R ¹ and R ² do not simultaneously become hydrogen atoms, and R ² and R ³ do not simultaneously become hydrogen atoms;

m, n, k and j are each independently an integer of 1 to 3;

When m, n, k, and j are 2 or 3, a plurality of R ¹ , R ³ in the formula may be the same or different from each other, and when m, n, k, j is 1, a plurality of R ² in the formula is may be the same or different from each other).

Here, 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 does not need to be comprised only with the structure of an alicyclic hydrocarbon, and the thing which has a chain structure in part is 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. In addition, in this specification, "organic group" means group containing a carbon atom, and the hetero atom may be included in the structure.

In the formula (p-1), as the monovalent hydrocarbon group having 1 to 10 carbon atoms for R ¹ , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, linear or branched alkyl groups, such as a nonyl group and a decyl group;

alkenyl groups such as a vinyl group and an allyl group;

alkynyl groups, such as an ethynyl group;

cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group;

Aryl groups, such as a phenyl group, a tolyl group, and a xylyl group;

Aralkyl groups, such as a benzyl group, a phenethyl group, and a styryl group, etc. are mentioned. Among these, it is preferable that R< ¹ > is a C1-C3 alkyl group.

Examples of the monovalent organic group for R ² include a monovalent hydrocarbon group having 1 to 10 carbon atoms, a group containing a hetero atom-containing group between the carbon-carbon bonds of the hydrocarbon group, a group in which the hydrocarbon group and a hetero atom-containing group are bonded; and a group in which at least one hydrogen atom in the group is substituted with a substituent, a cyano group, a formyl group, and the like.

Here, the hetero atom-containing group means a divalent or higher valence group having a hetero atom, for example, -O-, -CO-, -COO-, -CONR ^a - (R ^a is a hydrogen atom or has 1 to 6 carbon atoms) of an alkyl group, the same hereinafter), -NR ^a -, a trivalent nitrogen atom, -NR ^a CONR ^a -, -OCONR ^a -, -S-, -COS-, -OCOO-, -SO ₂ -, etc. are mentioned. . As a substituent, a halogen atom, a nitro group, a cyano group, a hydroxyl group etc. are mentioned, for example. Among the above, it is preferable that R< ² > is a C1-C6 alkyl group or a C6-C7 aryl group.

The C1-C6 alkyl group of R< ³ > may be linear or branched form may be sufficient as it. Examples of the monovalent nitrogen-containing heterocyclic group formed by bonding two R ³ to each other include groups in which the hydrogen atom bonded to the nitrogen atom of the nitrogen-containing heterocycle is removed. Specific examples of the nitrogen-containing heterocycle include a pyrrolidine ring and a piperizine ring, and these ring moieties may have a substituent such as a halogen atom or an alkyl group. R ³ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. X ¹ and Y ¹ are preferably oxygen atoms. 2 or 3 is preferable and, as for m, n, k and j, 3 is more preferable.

As the phosphorus-containing solvent, the compound represented by the formula (p-1) and the formula (p-3) in the above formulas (p-1) to (p-4) from the viewpoint of having a higher printability improvement effect. It is preferable that it is at least 1 sort(s) chosen from the group which consists of the compound which appears, and it is more preferable that it is a compound represented by said Formula (p-1).

Preferred specific examples of the phosphorus-containing solvent include, for example, each of the following formulas (p-1-1) to (p-1-7), (p-3-1) and (p-3-2) The compound etc. which appear are mentioned.

As a phosphorus containing solvent, since printability is more favorable, among the above, the compound represented by each of said Formula (p-1-1) - Formula (p-1-4) and Formula (p-3-1) is especially desirable. In addition, a phosphorus containing solvent can be used individually by 1 type or in combination of 2 or more type.

[Compound represented by Formula (1) above]

In the formula (1), examples of the alkyl group having 1 to 6 carbon atoms for R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group, and these may be linear or branched. Specific examples of the compound represented by the formula (1) include 4-formylmorpholine and 4-acetylmorpholine, and among these, 4-formylmorpholine is particularly preferable. In addition, the compound represented by said Formula (1) can be used individually by 1 type or in combination of 2 or more type.

[Compound represented by Formula (2) above]

In the formula (2), the description of R ⁴ in the formula (1) is applicable to the example of the alkyl group having 1 to 6 carbon atoms as R ⁵ . Examples of the alkanediyl group having 2 to 4 carbon atoms for R ⁶ include an ethylene group, a propanediyl group and a butanediyl group, and these may be linear or branched. Specific examples of the compound represented by the formula (2) include 3-methyl-2-oxazolidone, 3-ethyl-2-oxazolidone, 3-isopropyl-2-oxazolidone, N-methyl- 2-oxadinanone etc. are mentioned, Especially, it is especially preferable that it is 3-methyl-2- oxazolidone. In addition, the compound represented by said Formula (2) can be used individually by 1 type or in combination of 2 or more type.

[Compound represented by Formula (3) above]

In the formula (3), as the monovalent organic group of R ⁷ to R ¹⁰ , for example, an alkyl group having 1 to 10 carbon atoms, a group containing a hetero atom-containing group between the carbon-carbon bonds of the alkyl group, the alkyl group and hetero The group which the atom-containing group couple|bonded, the group etc. which substituted at least 1 hydrogen atom among these groups with the substituent are mentioned. About the specific example of a hetero atom containing group and a substituent, the description of R< ² > in said formula (p-1) is applicable. Further, R ⁷ to R ¹⁰ may be the same as or different from each other. R ⁷ to R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or —COR ^b (R ^b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). It is preferable that one of R ⁷ and R ¹⁰ is -COR ^b .

Specific examples of the compound represented by the formula (3) include 2-furaldehyde, 3-furaldehyde, 5-methyl-2-furaldehyde, 5-methyl-3-furaldehyde, and 4-methyl-2-furaldehyde. aldehyde, 5-hydroxymethyl-2-furaldehyde, etc. are mentioned, Among these, it is especially preferable that it is 5-methyl-2- furaldehyde. In addition, the compound represented by said Formula (3) can be used individually by 1 type or in combination of 2 or more type.

[Compound represented by the above formula (10)]

In the formula (10), examples of the alkyl group having 1 to 3 carbon atoms for R ¹¹ to R ¹³ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among these, a methyl group is preferable. Specific examples of the compound represented by the formula (10) include, for example, lactamide, N,N-dimethyllactamide, N,N-diethyllactamide, N-methyl-N-propyllactamide, and N-ethyllactamide. , N-isopropyl lactamide, and the like, and among these, N,N-dimethyl lactamide is particularly preferable. In addition, the compound represented by said Formula (10) can be used individually by 1 type or in combination of 2 or more type.

As a specific solvent, since printability (especially continuous printability) is more favorable, among the above, a phosphorus containing solvent, N,N- dimethylpropylene urea, the compound represented by the said Formula (1), and the said Formula (2) are represented It is preferable that it is at least 1 sort(s) chosen from the group which consists of compounds. In addition, as a specific solvent, 1 type can be used individually or in combination of 2 or more type.

[Other solvents]

The liquid crystal aligning agent of this invention may contain solvents (henceforth, it is also called "other solvents") other than a specific solvent. Specific examples of other solvents include, for example, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n- Butyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N -ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3 -Hexyloxy-N,N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, 1,3-dimethyl-2-imidazolidinone , N,N'-dimethylpropyleneurea, tetramethylurea, N-methyl-2-pyrrolidone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, γ-caprolactone, N,N -Diethylacetamide, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 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 monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, ethylene carbonate, propylene carbonate, and the like. In addition, as for another solvent, the said thing can be used individually by 1 type or in mixture of 2 or more types.

With respect to a specific solvent, it is good also considering all the solvents made into a liquid crystal aligning agent as a specific solvent, and good also considering a part as a specific solvent. With respect to the whole quantity of the solvent made to contain in a liquid crystal aligning agent, the content rate (the total amount, when using 2 or more types, the same) of a specific solvent becomes like this. Preferably it is 1-80 weight%, More preferably, it is 5-80 weight%. It is 70 weight%, More preferably, it is 10 to 60 weight%, Especially preferably, it is 20 to 60 weight%.

<Other ingredients>

Although the liquid crystal aligning agent of this invention contains the above polymer components and a solvent, it may contain other components as needed. As such other components, for example, a compound having at least one epoxy group in the molecule, a functional silane compound, a photopolymerizable compound, a surfactant, a filler, an antifoaming agent, a sensitizer, a dispersing agent, an antioxidant, an adhesion aid, an antistatic agent, a leveling agent and antibacterial agents. These blending ratios can be suitably set according to the compound to be blended in a range that does not impair the effects of the present invention.

Although the solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies to the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention considers a viscosity, volatility, etc., it is suitably selected, Preferably is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later and preferably heated to form a coating film that is a liquid crystal aligning film or a liquid crystal aligning film, but at this time, when the solid content concentration is less than 1% by weight , the film thickness of a coating film becomes too small, and it becomes difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and it is difficult to obtain a favorable liquid crystal aligning film, and the viscosity of a liquid crystal aligning agent increases and there exists a tendency for an application|coating characteristic to fall.

The range of especially preferable solid content concentration changes with the method used when apply|coating a liquid crystal aligning agent to a board|substrate. For example, in the case of spin coating, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. In the case of the offset printing method, it is especially preferable to make the solid content concentration into the range of 3 to 9 weight%, and to make the solution viscosity into the range of 12 to 50 mPa·s accordingly. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to be in the range of 1 to 5 wt%, and thereby the solution viscosity to be in the range of 3 to 15 mPa·s. The temperature at the time of preparing a liquid crystal aligning agent becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

<Liquid crystal alignment film and liquid crystal element>

The liquid crystal aligning film of this invention is formed with the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal element of this invention is equipped with the liquid crystal aligning film formed using said liquid crystal aligning agent. The drive mode of the liquid crystal in a liquid crystal element is not specifically limited, It can apply to various drive modes, such as a TN type, STN type, IPS type, FFS type, VA type, MVA type, PSA type. The liquid crystal element of this invention can be manufactured by the method including the following steps 1 - 3, for example. In step 1, the substrate used differs depending on the desired driving mode. Steps 2 and 3 are common to each drive mode.

[Step 1: Formation of a coating film]

First, a coating film is formed on a board|substrate by apply|coating the liquid crystal aligning agent of this invention on a board|substrate, and heating an application surface then.

(1-1) When manufacturing a TN-type, STN-type, VA-type, MVA-type or PSA-type liquid crystal element, two substrates on which a patterned transparent conductive film is formed are set as a pair, and A liquid crystal aligning agent is apply|coated, Preferably on the formation surface of a transparent conductive film, respectively by the offset printing method, the spin coating method, the roll coater method, or the inkjet printing method. As a board|substrate, For example, glass, such as float glass and soda glass;

A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly(alicyclic olefin) can be used. As a 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

After application|coating of a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated aligning agent, Preheating (prebaking) is preferably 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. Thereafter, a calcination (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, for thermal imidization of the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-300 degreeC, and post-baking time becomes like this. Preferably it is 5-200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 µm, more preferably 0.005 to 0.5 µm.

(1-2) When manufacturing an IPS type or FFS type liquid crystal display element, the electrode formation surface of the board|substrate on which the electrode which consists of the transparent conductive film or metal film patterned in the comb-tooth shape is formed, and the electrode which is not formed opposing A coating film is formed by apply|coating a liquid crystal aligning agent to one surface of a board|substrate, respectively, and heating each application surface then. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating condition after application, the film thickness, etc. are the same as in (1-1) above. As the metal film, for example, a film made of a metal such as chromium can be used.

In either case of said (1-1) and (1-2), after apply|coating a liquid crystal aligning agent on a board|substrate, the coating film used as a liquid crystal aligning film or a liquid crystal aligning film is formed by removing an organic solvent.

[Step 2: Orientation ability imparting treatment]

When manufacturing the liquid crystal display element of TN type, STN type, IPS type, or FFS type, the 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. Examples of the orientation ability imparting treatment include a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, or cotton, and a photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. have. On the other hand, when manufacturing a VA-type liquid crystal display element, although the coating film formed in the said process 1 can be used as a liquid crystal aligning film as it is, you may perform an orientation ability provision process with respect to the said coating film. The liquid crystal aligning film suitable for the liquid crystal display element of VA type can be used suitably also for the liquid crystal display element of PSA(Polymer Sustained Alignment) type.

[Step 3: Construction of liquid crystal cell]

A liquid crystal cell is manufactured by preparing two board|substrates with a liquid crystal aligning film as mentioned above, and arrange|positioning a liquid crystal between the board|substrates of 2 sheets opposingly arranged. In order to manufacture a liquid crystal cell, for example, (1) two board|substrates are opposingly arranged through a gap|interval so that a liquid crystal aligning film may oppose, and the peripheral part of two board|substrates is bonded using a sealing compound, The board|substrate surface and sealing A method of sealing an injection hole after injecting and filling a liquid crystal in the cell gap partitioned by the agent, (2) apply|coating a sealing compound to the predetermined place on one board|substrate on which the liquid crystal aligning film was formed, and also on the liquid crystal aligning film surface After a liquid crystal is dripped at several predetermined places, while bonding the other board|substrate so that a liquid crystal aligning film may oppose, the method (ODF system) etc. which spread a liquid crystal over the whole surface of a board|substrate are mentioned. It is preferable to remove the flow orientation at the time of liquid-crystal filling by cooling gradually to room temperature, after heating to the temperature which the liquid crystal used further takes an isotropic phase with respect to the manufactured liquid crystal cell.

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 them, a nematic liquid crystal is preferable, For example, Schiff base type liquid crystal, azoxy type liquid crystal, biphenyl type liquid crystal, phenylcyclohexane type liquid crystal, ester type liquid crystal. , terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cuban-based liquid crystal, and the like can be used. Moreover, you may add and use a cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, etc. to these liquid crystals, for example.

When manufacturing a PSA type liquid crystal display element, it carries out similarly to the above except for injecting|pouring or dripping a photopolymerizable compound with liquid crystal, and construct|constructs a liquid crystal cell. Thereafter, the liquid crystal cell is irradiated with light while a voltage of direct current or alternating current is applied between the conductive films of the pair of substrates. In addition, when a coating film is formed on a board|substrate using the liquid crystal aligning agent containing a photopolymerizable compound, it carries out similarly to the above, and constructs a liquid crystal cell, After that, between the electrically conductive films which a pair of board|substrates have, direct current or alternating current A liquid crystal element may be manufactured by passing through a step of irradiating light to the liquid crystal cell in a state in which a voltage of

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. As a polarizing plate bonded to the outer surface of a liquid crystal cell, a polarizing plate consisting of a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched with a cellulose acetate protective film, or a polarizing plate composed of the H film itself. can

The liquid crystal element of the present invention can be effectively applied to various devices, for example, a watch, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, and a smart phone. It can be used for various display devices, such as a phone, various monitors, and a liquid crystal television, a dimming film, etc. In addition, the liquid crystal element formed using the liquid crystal aligning agent of this invention can also be applied to retardation film.

(Example)

Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples.

The solution viscosity of each polymer solution in a synthesis example, the imidation ratio of a polyimide, a weight average molecular weight, and the epoxy equivalent were measured with the following method.

[Solution viscosity of polymer solution (mPa·s)]

About the solution adjusted to the polymer concentration of 10 weight% using the predetermined solvent, it measured at 25 degreeC using the E-type rotational viscometer.

[Imidation rate of polyimide]

A polyimide solution was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained < ¹ >H-NMR spectrum, the imidation rate [%] was calculated|required by following formula (1).

Imidization ratio [%] = (1-A ¹ /A ² x α) x 100 . . . (One)

(In formula (1), A ¹ is the peak area derived from protons of the NH group appearing in the vicinity of 10 ppm of the chemical shift, A 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)

[Weight Average Molecular Weight (Mw) of Polymer]

It is a polystyrene conversion value measured by the gel permeation chromatography in the following conditions.

Column: TSKgelGRCXLII manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40℃

Pressure: 68kgf/cm2

[Epoxy equivalent]

It measured by the hydrochloric acid-methylethyl ketone method described in JIS C2105.

<Synthesis of polymer>

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

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic dianhydride, 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine and 3,5- 10.5 g (0.02 mol) of diaminobenzoic acid cholestanyl (HCDA) was dissolved in 166 g of N-methyl-2-pyrrolidone (NMP), reacted at 60°C for 6 hours, and polyamic acid was contained in 20 wt% a solution was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 90 mPa·s.

Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7 weight%, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the polyimide (PI-) having an imidation rate of about 68% by replacing the solvent in the system with a new NMP (pyridine and acetic anhydride used in the dehydration ring closure reaction are removed out of the system by this operation; the same hereinafter). A solution containing 26% by weight of 1) was obtained. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 45 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The polyimide (PI-1) was obtained by washing|cleaning this deposit with methanol and drying it at 40 degreeC under reduced pressure for 15 hours.

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

22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 5.2 g (0.01 mol) of HCDA and 4.0 g (0.02 mol) of 4,4'-diaminodiphenylmethane (DDM) ) was dissolved in 157 g of NMP, and the reaction was performed at 60°C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 110 mPa·s.

Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7 weight%, 16.6 g of pyridine and 21.4 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 26 wt% of polyimide (PI-2) having an imidation ratio of about 82%. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 62 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The polyimide (PI-2) was obtained by washing|cleaning this deposit with methanol and drying it at 40 degreeC under reduced pressure for 15 hours.

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

2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2anhydride (BODA) 24.9g (0.10mol) as tetracarboxylic dianhydride, 8.6g PDA as diamine (0.08 mol) and HCDA 10.4g (0.02 mol) were melt|dissolved in NMP 176g, reaction was performed at 60 degreeC for 6 hours, and the solution containing 20 weight% of polyamic acids was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 103 mPa·s.

Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7 weight%, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 26 wt% of polyimide (PI-3) having an imidation rate of about 71%. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 57 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The polyimide (PI-3) was obtained by washing|cleaning this deposit with methanol and drying it at 40 degreeC under reduced pressure for 15 hours.

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

As tetracarboxylic dianhydride, 110 g (0.50 mole) of TCA and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) ) Naphtho [1,2-c] furan-1,3-dione 160 g (0.50 mol), PDA as diamine 91 g (0.85 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 25 g (0.10) mol) and 3,6-bis(4-aminobenzoyloxy)cholestane 25 g (0.040 mol), and 1.4 g (0.015 mol) of aniline as monoamine were dissolved in 960 g of NMP, followed by reaction at 60° C. for 6 hours. By doing so, a solution containing polyamic acid was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa·s.

Next, 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh γ-butyrolactone to obtain about 2,500 g of a solution containing 15% by weight of polyimide (PI-4) having an imidization rate of about 95%. The solution viscosity measured by fractionating a small amount of this solution, adding NMP, and making it into the solution of 10 weight% of polyimide density|concentrations was 70 mPa*s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The polyimide (PI-4) was obtained by washing|cleaning this deposit with methanol and drying it at 40 degreeC under reduced pressure for 15 hours.

[Synthesis Example 5: Synthesis of polyimide (PI-5)]

22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 8.6 g (0.08 mol) of PDA as diamine, 2.0 g (0.01 mol) of DDM and 4,4'-diamino-2,2'-bis(trifluoro 3.2 g (0.01 mol) of methyl) biphenyl was melt|dissolved in 324 g of NMP, reaction was performed at 60 degreeC for 4 hours, and the solution containing 10 weight% of polyamic acid was obtained.

Next, 360 g of NMP was added to the obtained polyamic acid solution, 39.5 g of pyridines and 30.6 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing 10% by weight of polyimide (PI-5) having an imidization rate of about 93%. The solution viscosity measured by aliquoting a small amount of the obtained polyimide solution was 30 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The polyimide (PI-5) was obtained by washing|cleaning this deposit with methanol and drying it at 40 degreeC under reduced pressure for 15 hours.

[Synthesis Example 6: Synthesis of polyimide (PI-6)]

The same method as in Synthesis Example 1 was followed except that the diamine used was changed to 0.08 mol of 3,5-diaminobenzoic acid (3,5DAB) and 0.02 mol of cholestanyloxy-2,4-diaminobenzene (HCODA). to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 80 mPa·s.

Next, imidation was performed by the method similar to the said synthesis example 1, and the solution containing 26 weight% of polyimide (PI-6) of about 65% of imidation ratio was obtained. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 40 mPa·s. Then, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. The polyimide (PI-6) was obtained by washing|cleaning this deposit with methanol and drying it at 40 degreeC under reduced pressure for 15 hours.

[Synthesis Example 7: Synthesis of polyamic acid (PA-1)]

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

[Synthesis Example 8: Synthesis of polyamic acid (PA-2)]

Except that the tetracarboxylic dianhydride used was 0.9 mol of pyromellitic dianhydride (PMDA) and 0.1 mol of CB, and the diamine was 0.2 mol of PDA and 0.8 mol of 4,4'-diaminodiphenyl ether (DDE) By the method similar to the said synthesis example 7, the polyamic acid solution of 10 weight% of solid content concentration and the solution viscosity of 170 mPa*s was obtained. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol and dried at 40°C under reduced pressure for 15 hours to obtain polyamic acid (PA-2).

[Synthesis Example 9: Synthesis of polyamic acid (PA-3)]

7.0 g (0.031 mol) of TCA as tetracarboxylic dianhydride and 13 g of a compound represented by the following formula (R-1) as diamine (corresponding to 1 mol per 1 mol of TCA) were dissolved in 80 g of NMP and heated at 60°C By reacting for 4 hours, a solution containing 20% by weight of polyamic acid (PA-3) was obtained. The solution viscosity of this polyamic acid solution was 2,000 mPa·s. In addition, the compound represented by a following formula (R-1) was synthesize|combined according to description of Unexamined-Japanese-Patent No. 2011-100099. Next, this polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol and dried at 40°C under reduced pressure for 15 hours to obtain polyamic acid (PA-3).

[Synthesis Example 10: Synthesis of polyorganosiloxane (APS-1)]

In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux cooling tube, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS), 500 g of methylisobutylketone and 10.0 g of triethylamine was added and mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then reacted at 80°C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to remove the reactive polyorganosiloxane (EPS-1). ) was obtained as a viscous transparent liquid. As a result of performing ¹ H-NMR analysis on this reactive polyorganosiloxane (EPS-1), a peak based on an epoxy group was obtained in the vicinity of a chemical shift (δ) = 3.2 ppm in the theoretical intensity range, and a side reaction of the epoxy group during the reaction It was confirmed that this did not happen. The weight average molecular weight (Mw) of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g/mol.

Next, in a 200 mL three-neck flask, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a reactive compound, and UCAT 18X ( 0.10 g of a brand name, San-Apro Co., Ltd. product) was put, and it reacted under stirring at 100 degreeC for 48 hours. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed with water 3 times, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain 9.0 g of liquid crystal aligning polyorganosiloxane (APS-1). . The weight average molecular weight (Mw) of the obtained polymer was 9,900.

[Synthesis Example 11: Synthesis of polyorganosiloxane (PS1)]

To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 32 g of p-styryltrimethoxysilane, 70 g of tetrahydrofuran, 33 g of triethylamine and 25 g of deionized water were added and mixed at room temperature. Then, while stirring under reflux, reaction was performed at 60 degreeC for 3 hours. After completion of the reaction, the organic layer was taken out, 60 g of diethylene glycol diethyl ether was added, and concentrated by heating. By concentrating until solid content concentration became 30 weight%, the diethylene glycol diethyl ether solution of polyorganosiloxane (PS1) was obtained.

[Synthesis Examples 12 and 13]

A solution of polyorganosiloxanes (PS-2) and (PS-3) in diethylene glycol diethyl ether was obtained in the same manner as in Synthesis Example 11 except that the input materials were as shown in Table 1 below. The weight average molecular weight (Mw) of the obtained polyorganosiloxane was put together in Table 1 below, and was shown.

In addition, in Table 1, the abbreviation of a raw material silane compound has the following meaning, respectively.

STTMS: p-styryltrimethoxysilane

ECETMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

PTMS: Phenyltrimethoxysilane

[Example 1]

<Preparation of liquid crystal aligning agent>

Using polyimide (PI-1) as a polymer, trimethyl phosphate (PTM), N-methyl-2-pyrrolidone (NMP) and butylcellosolve (BC) as solvents were added thereto so that the solvent composition was PTM :NMP:BC=20:40:40 (weight ratio), it was set as the solution of 6.5 weight% of solid content concentration. A liquid crystal aligning agent (S-1) was prepared by filtering this solution using the filter with a hole diameter of 1 micrometer. In addition, a liquid crystal aligning agent (S-1) is for manufacture of the liquid crystal display element of a vertical alignment type mainly.

<Evaluation of the swelling characteristic of the printing plate>

Using the said liquid crystal aligning agent (S-1), it evaluated about the ease (swelling characteristic) of the swelling of an APR board. An APR board is a resin board formed with the liquid photosensitive resin which an ultraviolet irradiation part hardens, and is generally used for the printing board of a liquid crystal aligning film printing machine. When a liquid crystal aligning agent and an APR board are made to contact, that an APR board does not swell easily at the time of printing does not penetrate|invade a liquid crystal aligning agent easily to an APR board, and it means that printability is favorable. Evaluation of a swelling characteristic was performed by immersing an APR board in a liquid crystal aligning agent for 1 day, and measuring the weight change of the APR board before and behind immersion. At this time, when the increase rate (swelling rate) of the weight of the APR plate was less than 4%, the APR plate hardly swells and was evaluated as good (○), and when the increase rate was 4% or more, the APR plate easily swells and was evaluated as poor (x). As a result, in this Example, the swelling ratio was 3.5%, and the swelling characteristic was "good (circle)". The swelling ratio was computed using the following formula (2).

Swelling rate [%] = ((W ² -W ¹ )/W ¹ )×100 . . . (2)

(In formula (2), W ¹ is the weight of the APR plate before immersion, and W ² is the weight of the APR plate after immersion).

<Evaluation of printability>

About the liquid crystal aligning agent (S-1) prepared above, the printability (continuous printability) at the time of performing the printing to a board|substrate continuously was evaluated. Evaluation was performed as follows. First, using a liquid crystal aligning film printing machine (manufactured by Nippon Photo Printing Machines Co., Ltd., Angstromer type "S40L-532"), the amount of liquid crystal aligning agent (S-1) dripped to the anilox roll was 20 drops reciprocally (about 0.2 Under the conditions of g), it printed on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film. Printing on the board|substrate was performed 20 times, using a new board|substrate at 1-minute intervals.

Next, the liquid crystal aligning agent (S-1) is dispensed (one way) on the anilox roll at intervals of 1 minute, and the operation (hereinafter referred to as an idle operation) of bringing the anilox roll into contact with the printing plate is performed 10 times in total (During this time, printing to a glass substrate was not performed). In addition, this idle operation is operation performed in order to make it perform printing of a liquid crystal aligning agent on a severe situation intentionally.

After 10 times of idling, the main printing was performed using the glass substrate next. In this printing, after idling, 5 substrates are put in at intervals of 30 seconds, each substrate after printing is heated (pre-baked) at 80° C. for 1 minute to remove the solvent, and then heated at 200° C. for 10 minutes (post-baking). ) to form a coating film having a film thickness of about 80 nm. The printability (continuous printability) was evaluated by observing this coating film with the microscope of 20 times the magnification. For evaluation, continuous printability is "good (○)" when no polymer precipitation is observed from the first printing after idling, and polymer precipitation is observed in the first printing after idling, but this printing is performed 5 times. Continuous printability is "possible (Δ)" when polymer precipitation is not observed during execution, and continuous printability "poor (x)" when polymer precipitation is observed even after repeating this printing 5 times. said As a result, in this Example, continuous printability was "good (circle)". Moreover, in the liquid crystal aligning agent with favorable printability, experiment knows that precipitation of a polymer improves (disappears) while injecting|throwing-in a board|substrate continuously. Furthermore, as a result of changing the number of times of an idle run to 15 times, 20 times, and 25 times, about each, carrying out similarly to the above and evaluating the printability of a liquid crystal aligning agent, in this Example, 15 times and 20 times of an idle run When the circuit was performed, it was "good (○)", and when it was 25 times, it was "possible (Δ)".

[Examples 2-31 and Comparative Examples 1-5]

Liquid crystal aligning agents (S-2) to (S-31) and (S-2) to (S-31) and ( SR-1) to (SR-5) were prepared, respectively. Moreover, about each liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated the swelling characteristic and printability of a printing plate. Those results are shown in Table 2 below.

In Table 2, about those using 2 types of polymers as a polymer component (Examples 18-31), the usage ratio (weight ratio) of each polymer with respect to 100 weight part of total amounts of the used polymer was collectively shown. Among each liquid crystal aligning agent, (S-2)-(S-17), (SR-1)-(SR-5) are mainly a vertical alignment type, (S-18)-(S-23) mainly TN type. , (S-24) are mainly for manufacturing an IPS type liquid crystal display element, (S-29) to (S-31) are mainly for manufacturing a vertical alignment type liquid crystal display element by a photo-alignment method, (S-25) -(S-28) are mainly for manufacture of the liquid crystal display element of a PSA system. In Table 2, the numerical value of a solvent composition shows the compounding ratio (weight ratio) of each compound with respect to the total amount of the solvent used for preparation of a liquid crystal aligning agent (the same also about the following Tables 3 - Table 5). The symbols of the solvent composition have the following meanings, respectively.

a: trimethyl phosphate

b: triethyl phosphate

c: hexamethyl phosphate triamide

d: N-methyl-2-pyrrolidone

e: N-ethyl-2-pyrrolidone

f: γ-butyrolactone

g: γ-valerolactone

h: δ-valerolactone

i: N,N-diethylacetamide

j: butyl cellosolve

k: diethylene glycol diethyl ether

l: propylene glycol monomethyl ether acetate

[Examples 32-52]

Liquid crystal aligning agents (S-32) to (S-52) were each prepared in the same manner as in Example 1, except that the polymer to be used and the type and composition of the solvent were changed as shown in Table 3 below. prepared Moreover, about each liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated the swelling characteristic and printability of a printing plate. Those results are shown in Table 3 below.

In Table 3, about what used 2 types of polymers as a polymer component (Examples 40-43, 50-52), the usage ratio (weight ratio) of each polymer with respect to 100 weight part of total amounts of the used polymer was collectively shown. Moreover, (S-32)-(S-39), (S-44)-(S-49) are mainly vertical alignment type, (S-40)-(S-43), (S-43) among each liquid crystal aligning agent. S-50) to (S-52) are mainly for the manufacture of a TN type liquid crystal display element. In Table 3, the symbol of a solvent composition has the following meaning, respectively. d and j are the same as in Table 2 above.

m: N,N-dimethylpropylene urea

n: 4-formylmorpholine

o: 3-methyl-2-oxazolidone

p: tetrahydro-4H-pyran-4-one

r: tetramethylene sulfoxide

s: 3-methylcyclohexanone

t: 4-methylcyclohexanone

[Examples 53-56]

Liquid crystal aligning agents (S-53) to (S-56) were prepared in the same manner as in Example 1, except that the polymer component to be used and the type and composition of the solvent were changed as described in Table 4 below. each prepared. Moreover, about each liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated the swelling characteristic and printability of a printing plate. Those results are shown in Table 4 below.

In Table 4, about those using two types of polymers as polymer components (Examples 55 and 56), the usage ratio (weight ratio) of each polymer with respect to 100 weight part of total amounts of the used polymer was collectively shown. In addition, in each liquid crystal aligning agent, (S-53) and (S-54) are mainly for manufacture of a TN-type liquid crystal display element, (S-55) and (S-56) mainly for a vertical alignment type. In Table 4, the symbol of a solvent composition has the following meaning, respectively. d and j are the same as in Table 2 above.

q: 5-methyl-2-furaldehyde

u: N,N-dimethyllactamide (compound represented by the following formula (10-1))

[Examples 57 to 60]

Liquid crystal aligning agents (S-57) to (S-60) were each prepared in the same manner as in Example 1, except that the type and composition of the polymer to be used and the solvent were changed as shown in Table 5 below, respectively. prepared Moreover, about each liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated the swelling characteristic and printability of a printing plate. Those results are shown in Table 5 below. In addition, in Table 5, the numerical value of the column of the polymer component shows the usage ratio (weight ratio) of each polymer with respect to 100 weight part of total amounts of the polymer used. Symbols (d, m, j) of the solvent composition are the same as in Tables 2 and 3 above.

It turned out that it is hard to swell a printing plate, and all the liquid crystal aligning agents (Examples 1-60) containing the said specific solvent from said result also have favorable continuous printability. On the other hand, the thing of the comparative example which does not contain the said specific solvent was a result inferior to an Example in any of swelling characteristic and continuous printability.

Claims (6)

a polymer component;
Liquid crystal aligning agent containing the compound represented by following formula (p-1):

(In formula (p-1), X ¹ and Y ¹ are each independently an oxygen atom or a sulfur atom;
R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent organic group;
provided that R ¹ and R ² may be bonded to each other to form a ring;
R ¹ and R ² do not simultaneously become hydrogen atoms;
m is an integer of 1 to 3;
When m is 2 or 3, a plurality of R ¹ in the formula may be the same or different from each other, and when m is 1, a plurality of R ² in the formula may be the same or different from each other). delete According to claim 1,
The liquid crystal aligning agent containing at least 1 sort(s) of polymer chosen from the group which consists of polyamic acid, polyamic acid ester, a polyimide, and polyorganosiloxane as said polymer component. 4. The method of claim 1 or 3,
The liquid crystal aligning agent whose content rate of the compound represented by said Formula (p-1) is 1-80 weight% with respect to the whole quantity of the solvent in a liquid crystal aligning agent. delete delete