KR20140059124A - Liquid crystal aligning agent, liquid crystal alignment film, and retardation film and liquid crystal cell of liquid crystal display device - Google Patents

Abstract

Provided is a liquid crystal aligning agent capable of improving application properties (printing properties) while granting a liquid crystal alignment film having liquid crystal alignment properties, electrical characteristics, heat-resisting properties, etc. The liquid crystal aligning agent contains at least one polymer selected from the group consisting of polyorganosiloxanes, polyamides, poly(thio)esters and (meth)acrylic acid copolymers. The polymer has a divalent group represented by the formula (1), wherein Q is a tetravalent organic group, Y1 and Y2 are divalent organic groups, respectively, and [*] are bonding hands bonded to polymer chains, respectively.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal cell, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal cell,

The present invention relates to a liquid crystal aligning agent.

The present invention provides a liquid crystal aligning agent having properties exceeding liquid crystal aligning agents containing a partially imidized polymer of polyamic acid.

The liquid crystal display element is provided with a liquid crystal alignment film having a function of aligning the liquid crystal molecules in a predetermined direction. This liquid crystal alignment film is generally formed through a step of applying (printing) a liquid crystal aligning agent containing a polymer onto a substrate. As the polymer contained in the liquid crystal aligning agent, imidized polymers of polyamic acid, polyamic acid, polyamide, polyester, and polyorganosiloxane are known (Patent Documents 1 to 3).

Of these, liquid crystal aligning agents containing a polyamic acid as a polymer have excellent applicability (printability), but there is room for improvement in the electrical characteristics and heat resistance of the resulting liquid crystal alignment film. A liquid crystal aligning agent containing a polyamic acid imidized polymer gives a liquid crystal alignment film excellent in liquid crystal alignability and electrical characteristics, but the application property of the liquid crystal aligning agent itself is not sufficient. Since the polyamide, polyester or polyorganosiloxane is excellent in solubility in a general-purpose organic solvent, the liquid crystal aligning agent containing them is excellent in the coating property, but the liquid crystal alignment property of the formed liquid crystal alignment film is not sufficient.

Japanese Patent No. 3764250 Specification Japanese Patent No. 3912859 Specification Japanese Patent No. 3757514 Japanese Laid-Open Patent Publication No. 2010-97188

 "UV curable liquid and its application", Liquid Crystal, Vol. 3, No. 1 (1999), pp. 34-42  T.J.Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)  F. Nakano et al., JPN.J.Appl.Phys.vol.19, p2013 (1980)

Disclosure of the Invention The present invention has been made in order to overcome the above-mentioned problems, and it is an object of the present invention to provide a liquid crystal alignment film having improved liquid crystal alignability, electrical characteristics, heat resistance, etc., And the like.

According to the present invention,

A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyorganosiloxane, polyamide, poly (thio) ester and (meth) acrylic acid copolymer, wherein the polymer is represented by the following formula And has a divalent group. ≪ RTI ID = 0.0 >

(In the formula (1), Q represents a tetravalent organic group, Y ¹ and Y ² each represent a divalent organic group, and "*" represents a bonding bond bonded to the polymer chain, respectively.

In the present specification, the polymer satisfying the above conditions is hereinafter also referred to as a " specific polymer ".

According to the present invention, there is provided a liquid crystal aligning agent capable of imparting a liquid crystal alignment film excellent in coating property (printability) and excellent in liquid crystal alignability, electrical characteristics, heat resistance and the like. That is, the polymer contained in the liquid phase aligning agent of the present invention has a polymer skeleton having high solubility which contributes to the coating property of the liquid crystal aligning agent, and an imidazole ring structure contributing to the liquid crystal alignability, electrical characteristics and heat resistance of the resulting liquid crystal alignment film It has an excellent balance between the two.

1 is a schematic cross-sectional view for explaining the structure of an electrode pair of an FFS type liquid crystal display device manufactured in Example FFS-1.
2 is a schematic plan view for explaining a comb-like structure of a top electrode included in the FFS type liquid crystal display device manufactured in Example FFS-1.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention contains a specific polymer.

≪ Specific polymer &

The specific polymer in the present invention is at least one kind of polymer selected from the group consisting of polyorganosiloxane, polyamide, poly (thio) ester and (meth) acrylic acid copolymer, Lt; / RTI >

In the divalent group represented by the above formula (1), two bonded hands marked with " * " are bonded to the polymer chain, which means that the divalent group is present in the main chain of the polymer, Quot; is meant to be present as part of the cross-linking, either red or three-dimensionally. That is, this divalent group is not present as a side chain or a part of the polymer, or a side chain or a part of the cross-linking structure. However, the specific polymer may be such that the divalent group represented by the above formula (1) is present in the main chain or the crosslinked structure of the polymer, and the side chain of the polymer or a part thereof or the side chain of the crosslinked structure or a part thereof is inhibited from having a homogeneous structure It is not.

That the ^3-mole / g than ^- the content of the divalent group represented by the formula (1) in the specific polymer is, 1.0 × 10 ^{- 4} mol / g, and preferably, 3.0 × 10 ^-4 ~2.0 × 10 or more desirable.

Specific polymers include, for example,

A polyamide obtained by reacting a diamine with a compound represented by the following formula (C) (hereinafter referred to as " compound (C) ");

A poly (thio) ester obtained by reacting at least one member selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound with a compound (C);

A poly (thio) ester obtained by reacting a compound represented by the following formula (E) (hereinafter referred to as "compound (E)") with dicarboxylic acid;

(Meth) acrylic acid copolymer obtained by addition polymerization of a mixture of a polymerizable unsaturated compound containing a (meth) acrylic acid and a compound represented by the following formula (A) (hereinafter referred to as "compound (A)");

, A polyorganosiloxane obtained by hydrolyzing and condensing a silane compound containing a compound represented by the following formula (S) (hereinafter referred to as " compound (S) "),

(In the formula (C), Q, Y ¹ and Y ² have the same meanings as in the formula (1), and n 3 and n 4 each independently is 1 or 2);

(Wherein Q, Y ¹ and Y ² have the same meanings as in the above formula (1), and Z ¹ and Z ² each independently represent a hydroxyl group, a thiol group or an epoxy group) ;

(In the formula (A), Q, Y ¹ and Y ² are the same as those in the formula (1), and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group);

(Wherein Q, Y ¹ and Y ² are the same as those in the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms or a X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom; and n 1 and n 2 are each independently an integer of 1 to 3).

As apparent from the above formula, the divalent group represented by the formula (1) is derived from the compound (C), (E), (A) or (S). These compounds can be obtained by reacting a tetracarboxylic acid dianhydride represented by the following formula (T-1) with a primary amine compound as described later. Therefore, the compound represented by the formula (T) The units appearing (thus, the unit represented by the following formula (T) in the compound (C), (E), (A) or (S)) can be obtained by reacting a tetracarboxylic acid dianhydride represented by the following formula (T-1) The resulting four-valence group is:

(In the formula (T), Q has the same meaning as in the formula (1), and "*" indicates a bonding hand);

(In the formula (T-1), Q is the same as that in the formula (1)).

The tetravalent group derived from the tetracarboxylic dianhydride represented by the formula (T-1) means a tetravalent group obtained by removing all two oxygen atoms constituting the ring by the tetracarboxylic dianhydride.

As the tetracarboxylic acid dianhydride represented by the above formula (T-1), known tetracarboxylic acid dianhydrides used for producing the polyamic acid or imidized polymer contained in the liquid crystal aligning agent can be used without particular limitation have. Examples of such tetracarboxylic acid dianhydrides include tetracarboxylic dianhydrides described in Patent Document 4 (Japanese Unexamined Patent Application Publication No. 2010-97188). Particularly preferred tetracarboxylic acid dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: Dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyro And at least one selected from the group consisting of melanic acid dianhydride.

The primary amine compound to be reacted with the above tetracarboxylic acid dianhydride is described in the description of the compound (C), (E), (A) or (S).

[Synthesis of Compound (C)

The compound (C) can be obtained, for example, by reacting the tetracarboxylic acid dianhydride represented by the formula (T-1) with an amino acid. This amino acid is a compound having one primary amino group and one or two carboxyl groups in the molecule. In this case, the formula (C) group Y ¹ (Y ¹ group Thus in the formula (1)) of the can, by removing the amino and carboxy from the amino acid is not a divalent or trivalent group is obtained.

Examples of the amino acid include one having a carboxy group such as glycine, alanine, leucine, isoleucine, phenylalanine, valine, 4-aminobutyric acid and the like;

Examples of the carboxy group having two carboxy groups are asparagine acid, glutamic acid, 2-aminoadipic acid, carboxystaine, 2,3-dicarboxy aniline, 3,4-dicarboxy aniline, Naphthalene, 4-amino-1,2-dicarboxy naphthalene, 5-amino-1,2-dicarboxy naphthalene, 6-amino- Amino-2,3-dicarboxy naphthalene, 5-amino-2,3-dicarboxy naphthalene, 6- Amino-2,3-dicarboxy naphthalene, 7-amino-2,3-dicarboxy naphthalene, 8-amino-2,3-dicarboxy naphthalene, etc., and at least one selected from these may be used .

The reaction of the tetracarboxylic acid dianhydride represented by the formula (T-1) with the amino acid can be carried out by heating the mixture of these compounds, preferably in a suitable solvent.

The ratio of the two compounds in this reaction is preferably 1.0 to 4.0 moles, more preferably 1.5 to 3.0 moles, and more preferably 1.8 to 2.5 moles, in terms of the ratio of the amino acid to 1 mole of the tetracarboxylic acid dianhydride .

As the solvent used in this reaction, an organic solvent is preferable, and for example, non-protonic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like can be used .

Specific examples of these organic solvents include non-protonic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Butyrolactone, tetramethylurea, hexamethylphosphoric triamide, pyridine, 2-picoline, 3-picoline, 4-picoline and the like;

As the phenol derivative, for example, m-cresol, xylenol, halogenated phenol and the like;

As the alcohol, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like;

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like;

As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate and the like;

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetraethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, Hydrofuran and the like;

As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate and diisopentyl ether, and at least one Is preferably used.

The solvent is preferably used in an amount of 50 to 5,000 parts by weight, more preferably 100 to 3,000 parts by weight, and further preferably 100 to 2,000 parts by weight, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and amino acid desirable.

The reaction of the tetracarboxylic acid dianhydride with the amino acid is preferably carried out at a temperature of 50 to 300 캜, more preferably 80 to 200 캜, preferably 0.1 to 10 hours, more preferably 0.1 to 20 hours All. Optionally, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the range of the temperature and the reaction time.

[Synthesis of Compound (E)

Compound (E) during, Z ¹ and Z ² is a hydroxy group or a thiol group compounds, Z ¹ and according to the type of Z ^2, for example, tetracarboxylic acid dianhydride represented by the above formula (T-1) and, Amino alcohols, aminophenols or aminothiols. In this case, the group (group Y ¹ in accordance the formula ⁽¹⁾⁾ Y 1 in the formula (E) is a divalent group obtained by removing an amino group, a hydroxyl group or a thiol group from the amino alcohol or amino thiol .

Examples of the aminoalcohol include 2-aminoethanol, 3-aminopropanol, 4-aminobenzyl alcohol, 2- (4-aminophenyl) ethanol and the like;

Examples of the aminophenol include 4-aminophenol and the like;

Examples of the aminothiol include 3-thiol aniline, 4-thiol aniline, 1-thiol-3-aminopropane and the like.

The reaction of the tetracarboxylic acid dianhydride with the amino alcohol, aminophenol or aminothiol can be carried out by heating the mixture of these compounds, preferably in a suitable solvent.

The use ratio of the two compounds in this reaction is preferably 1.0 to 4.0 mol, more preferably 1.5 to 3.0 mol, in terms of the ratio of the amino alcohol, aminophenol or aminothiol to 1 mol of the tetracarboxylic acid dianhydride , More preferably 1.8 to 2.5 mol, per 1 mol of the catalyst.

As the solvent used in this reaction, the same solvents as those exemplified above can be used as the solvent which can be used in the synthesis of the compound (C). The use ratio of the solvent is preferably 50 to 5,000 parts by weight, more preferably 100 to 3,000 parts by weight, based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and the amino alcohol, aminophenol or aminothiol , More preferably from 100 to 2,000 parts by weight.

This reaction is preferably carried out at a temperature of 50 to 300 캜, more preferably 80 to 200 캜, preferably 0.1 to 10 hours, more preferably 0.1 to 20 hours. Optionally, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the range of the temperature and the reaction time.

Thus, a diol compound in which the groups Z ¹ and Z ² are each a hydroxyl group or a dithiol compound in which the groups Z ¹ and Z ² are each a thiol group are obtained in the above formula (E).

The compound in which Z ¹ and Z ² in the compound (E) are each an epoxy group can be obtained, for example, by reacting the diol compound or dithiol compound obtained as described above with a compound having an epoxy group and a halogen atom . In this case, the formula (E) group Y ¹ (thus group Y ¹ in the formula (1)) is a divalent group Y ¹ in the resulting diol compound or dithiol compound as described above in the , A divalent group formed by bonding an epoxy group and a divalent group obtained by removing an epoxy group and a halogen atom from a compound having a halogen atom by an ether bond.

Here, as the epoxy group, any of an oxiranyl group and an oxetanyl group may be used. As the compound having an oxiranyl group and a halogen atom, for example, epichlorohydrin, 2- (chloromethyl) -1,2-epoxypropane, 2- (chloromethyl) -1,2-epoxybutane, 2- 1,2-epoxypropane, 2- (bromomethyl) -1,2-epoxybutane, and the like;

Examples of the compound having an oxetanyl group and a halogen atom include 3- (chloromethyl) oxetane, 3- (chloromethyl) -3-methyloxetane, 3- (bromomethyl) oxetane, 3- Methyl) -3-methyloxetane and the like;

(Meth) acrylic group and a halogen atom, for example, (meth) acryl chloride and the like, and at least one selected from the above can be used.

This reaction can be carried out by heating a mixture of the diol compound or dithiol compound thus obtained with a compound having an epoxy group and a halogen atom, preferably in the presence of a suitable catalyst, preferably in a suitable solvent .

The ratio of the diol compound or dithiol compound to the compound having an epoxy group and a halogen atom is preferably 0.5 to 10 moles, more preferably 1.0 to 3.0 moles, per mole of the former , Particularly 1.8 to 2.5 mol, per mol of the compound of formula

Examples of the catalyst that can be used in this reaction include quaternary amine salts and specific examples thereof include tetrabutylammonium chloride and tetrabutylammonium bromide. The use ratio of the catalyst is preferably 20 parts by weight or less, more preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the diol compound or the dithiol compound.

The solvent used here is preferably an organic solvent, and the same solvent as that exemplified above can be used as the solvent used in the synthesis of the compound (C).

The solvent is preferably used in an amount of 10 to 3,000 parts by weight, more preferably 50 to 2,000 parts by weight, more preferably 50 to 2,000 parts by weight, based on 100 parts by weight of the total amount of the diol compound or the dithiol compound and the compound having an epoxy group and a halogen atom. More preferably 1,000 parts by weight.

This reaction is preferably carried out at a temperature of -78 to 60 캜, more preferably -78 to 40 캜, preferably 0.5 to 30 hours, more preferably 2 to 15 hours. Optionally, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the range of the temperature and the reaction time.

[Synthesis of Compound (A)

The compound (A) can be obtained, for example, by the reaction of a diol compound in which the groups Z ¹ and Z ² in the formula (E) are each a hydroxyl group with (meth) acrylic acid. In this case, the group (group Y ¹ in the formula according ⁽¹⁾⁾ Y 1 in the formula (A) is, becomes equal to the group Y ¹ in the compound (E) used as a raw material. Here, it is preferable that the (meth) acrylic acid is acid-chlorinated by a known method and then supplied to the reaction.

The ratio of the diol compound (E) to the (meth) acrylic acid acidified with acid chloride is preferably 0.5 to 10 moles of (meth) acrylic acid per mole of the compound (E) More preferably from 1.0 to 3.0 mol, and particularly preferably from 1.8 to 2.5 mol.

The reaction can be carried out by dissolving the compound (E) as a diol compound in an appropriate solvent, preferably dropping the acid chloride-containing (meth) acrylic acid in a suitable solvent while dissolving it in a suitable solvent.

As the solvent usable here, the same solvents as those exemplified above can be used as the solvent which can be used in the synthesis of the compound (C). The use ratio of the solvent is preferably such that the ratio of the total weight of the diol compounds (E) and (meth) acrylic acid in the reaction solution is 0.5 to 50 wt%, preferably 1 to 30 wt% Ratio is more preferable.

The reaction is preferably carried out at a temperature of -100 to 100 ° C, more preferably -20 to 40 ° C. Here, in the case of reacting (meth) acrylic acid as it is, it is preferable to set the reaction temperature to a room temperature (25 캜) or more;

In the case of reacting (meth) acrylic acid with an acid chloride, the reaction temperature is preferably lower than the room temperature. The reaction time is preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours. When the reaction is carried out by dropwise addition of (meth) acrylic acid (preferably in the form of an acid chloride), this reaction time starts the measurement from the end of the dropwise addition.

[Synthesis of Compound (S)

The compound (S) can be produced, for example, by dehydrating a diol compound in which the groups Z ¹ and Z ² are each a hydroxyl group in the above formula (E) to form a double bond at the terminal thereof and then subjecting the double bond to a hydrolysis reaction And then adding an alkoxysilane compound. In this case, the group (group Y ¹ in the formula according ⁽¹⁾⁾ Y 1 in the formula (S) is, becomes equal to the group Y ¹ in the compound (E) used as a raw material.

The dehydration reaction of the diol compound can be preferably carried out by bringing the diol compound into contact with sulfuric acid in a suitable organic solvent.

Examples of the organic solvent usable herein include acetic acid, acetic anhydride, tetrahydrofuran, acetonitrile, chloroform, dichloromethane, diethyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, dimethylformamide, Dimethyl sulfoxide, hexane, and 1,4-dioxane. The use ratio of the organic solvent is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight, per 100 parts by weight of the compound (E) which is the diol compound.

The use ratio of sulfuric acid is preferably 0.0001 to 100 parts by weight, more preferably 0.001 to 10 parts by weight, per 100 parts by weight of the compound (E) which is the diol compound. The sulfuric acid is preferably added to the reaction system gradually.

The dehydration reaction of the diol compound is preferably carried out at a temperature of 0 to 300 캜, more preferably 25 to 150 캜, preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours. When the reaction is carried out by dropwise addition of sulfuric acid, the above reaction time starts to be measured from the end of the dropwise addition.

The reaction of adding the alkoxysilane compound to the dehydration product thus obtained can be carried out according to a known hydroxylation reaction.

The alkoxysilane compound used herein is a compound having at least one H-Si bond and at least one alkoxy-Si bond, and specifically includes, for example, dimethylmethoxysilane, dimethylethoxysilane, methyldimethoxy Silane, diethylmethoxysilane, organohydrogensilane such as diphenylmethoxy, and the like, and at least one selected from the above can be used.

The use ratio of the alkoxysilane compound is preferably 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol, and particularly preferably 1.8 to 2.5 mol, as a ratio of the alkoxysilane compound to 1 mol of the dehydration product.

This hydroxylation reaction is preferably carried out in the presence of a suitable catalyst, preferably in an appropriate organic solvent.

Examples of the catalysts usable herein include chloroplatinic acid, Wilkinson complex (RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ), Carsted catalyst (vinylsiloxane complex of chloroplatinic acid), Spire catalyst (alcohol of chloroplatinic acid Solution), and the like, and at least one selected from these can be used. The use ratio of the catalyst is preferably 0.01 to 200 micro mol (mu mol), more preferably 0.05 to 50 micro mol, per 1 mol.

Examples of the organic solvent usable herein include hydrocarbons, halogenated hydrocarbons, ethers, and esters. Of these, hydrocarbons are preferably used, and it is particularly preferable to use at least one selected from the group consisting of toluene, heptane, hexane, benzene, toluene and xylene. The use ratio of the organic solvent is preferably 10 to 2,000 parts by weight, more preferably 50 to 1,000 parts by weight, per 100 parts by weight of the dehydration product.

The hydroxylation reaction is preferably carried out at a temperature of 30 to 200 캜, more preferably 50 to 120 캜, preferably 0.1 to 60 hours, more preferably 0.5 to 40 hours.

[Production of Specific Polymer]

Next, a method for producing a specific polymer in the present invention will be described. The liquid crystal aligning agent containing the specific polymer prepared by the method described below using the monomers exemplified below is a liquid crystal alignment film formed by rubbing the coating film, and is a liquid crystal alignment film of TN type, STN type, IPS type, FFS Type liquid crystal display device. However, when a monomer having a pretilt angle-generating group is used as at least a part of the monomer, the liquid crystal aligning agent containing the specific polymer is a liquid crystal alignment film formed without rubbing treatment on the coating film, Applicable to devices;

When a monomer having a photo-alignment group is used as at least a part of the monomer, the liquid crystal alignment film formed by photoirradiation of the coating film can be suitably applied to a liquid crystal display device of any form.

The pretilt angular expression group and the photo-orientable group will be described later.

(1) Production of polyamide

The polyamide which is an example of the specific polymer in the present invention can be obtained by reacting the diamine with the compound (C) obtained as described above. Here, it is preferable that the compound (C) is subjected to acid chloride formation by a known method and then to the reaction.

Examples of the diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, ethyl 2- (2,4-diaminophenoxy) methacrylate, dodecaneoxy- Diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Stearyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 Bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1- Pe ) And the like 4-heptyl cyclohexane, can be used one or more selected from these into.

The compound (C) may be used alone, or the compound (C) may be used in combination with other polyvalent carboxylic acids. Examples of other polyvalent carboxylic acids used herein include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, Isophthalic acid, and the like, and at least one selected from these may be used.

When the compound (C) is used in combination with other polyvalent carboxylic acids, the proportion of the compound (C) to be used is preferably 5 mol% or more with respect to the total amount of the compound (C) Mol% or more.

The ratio of the diamine to the diamine is preferably from 0.7 to 1.2 mol, more preferably from 0.9 to 1.1 mol, relative to 1 mol of the total of the carboxy group of the compound (C) and the other polyvalent carboxylic acid .

The reaction can be carried out by dissolving the diamine in an appropriate solvent to obtain a mixture of the compound (C) or the compound (C) with another polyvalent carboxylic acid (hereinafter, referred to collectively as "polyvalent carboxylic acids" Preferably an acid chloride, and then, if necessary, dropwise in a suitable solvent (for example, tetrahydrofuran).

As the solvent usable here, the same solvents as those exemplified above can be used as the solvent which can be used in the synthesis of the compound (C). The use ratio of the solvent is preferably such that the ratio of the total weight of the polyvalent carboxylic acids and the diamine in the reaction solution is 3 to 50% by weight.

The reaction is preferably carried out at a temperature of -100 to 200 캜, more preferably -20 to 150 캜. When reacting the polyvalent carboxylic acids as they are, it is preferable to set the reaction temperature to room temperature (25 캜) or more;

When the polyvalent carboxylic acids are reacted after the acid chloride-forming reaction, the reaction temperature is preferably lower than the room temperature. The reaction time is preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours. When the reaction is carried out by dropwise addition of polyvalent carboxylic acids (preferably in the form of an acid chloride), this reaction time starts to be measured from the end of the dropwise addition.

The Mw of the polyamide as the specific polymer in the present invention (weight average molecular weight in terms of polystyrene measured by gel permeation chromatography; hereinafter the same) is preferably 1,000 to 500,000, more preferably 5,000 to 300,000 to be.

(2) Preparation of poly (thio) ester

The poly (thio) ester which is an example of the specific polymer in the present invention is obtained by reacting the compound (C) with at least one member selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound; Or by reacting the compound (E) with dicarboxylic acid.

Examples of the diol compound include 3,6-dihydroxycholestane, 3,5-dihydroxybenzoic acid-3-cholestanyl, 3,5-dihydroxybenzoic acid, ethylene glycol, Diol, 1,4-butanediol, 1,3-butanediol, 1,4-cyclohexanediol, phenyl-1,2-ethanediol, dimethyl- methylhydroquinone, t-butylhydroquinone, chlorohydroquinone, 2-methoxyhydroquinone, phenylhydroquinone, 2,3-dimethylhydroquinone, 2,3-dimethylhydroquinone, 2,3- , 5,6-tetramethylhydroquinone, 2,3,5,6-tetrachlorohydroquinone, resorcin, 2-methylresorcin, 4-hexylresorcin, 5-phenylresorcin, Roxynaphthalene;

Examples of the dithiol compound include benzene-1,4-dithiol, 2-methylpropane-1,1-dithiol, butane-1,1-dithiol, 1-dithiol, 3-methylbutane-1,1-dithiol, hexane-1, Dithiol, 2-methylhexane-1,1-dithiol, 3-methylhexane-1,1-dithiol, and the like;

Examples of the diepoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, and the like , And at least one selected from the above can be used, respectively.

When the poly (thio) ester is synthesized by reacting at least one member selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound with the compound (C), the compound (C) (C) and other polyvalent carboxylic acids may be used in combination. As other polyvalent carboxylic acids to be used herein, the same polyhydric carboxylic acids as those exemplified above can be used as polyvalent carboxylic acids which can be used together with the compound (C) in the synthesis of polyamide. When the compound (C) is used in combination with other polyvalent carboxylic acids, the proportion of the compound (C) to be used is preferably 5 mol% or more with respect to the total amount of the compound (C) Mol% or more.

The synthesis reaction of the poly (thio) ester by reacting the compound (C) with at least one member selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound is carried out by using a diol compound, a dithiol compound, And a diepoxy compound can be used in place of the polyamide compound of the present invention.

As the compound (E) to be used when the synthesis of the poly (thio) ester is performed by the method of reacting the compound (E) and the dicarboxylic acid, it is preferable that all of Z ¹ and Z ² in the formula (E) Diepoxy compounds are preferred. The compound (E) which is a diepoxy compound may be used alone, or the compound (E) and other diepoxy compounds may be used in combination. As the other diepoxy compounds used herein, the same diepoxy compounds as those exemplified above can be used as the diepoxy compounds which can be used in the former method for synthesizing poly (thio) esters. When the compound (E) and the other diepoxy compound are used in combination, the use ratio of the compound (E) is preferably 5 mol% or more with respect to the total amount of the compound (E) and the other diepoxy compound, More preferably 10 mol% or more.

The diepoxy compound (E) and other diepoxy compounds are preferably dioxiranyl compounds, respectively.

As the dicarboxylic acid in the present reaction, the same polycarboxylic acid as the dicarboxylic acid exemplified above may be used as the polyvalent carboxylic acid which can be used together with the compound (C) in the synthesis of the polyamide.

The synthesis reaction of the poly (thio) ester by reacting the compound (E) and the dicarboxylic acid can be carried out by using the compound (E) (or a mixture of the compound (E) and the other diepoxy compound) instead of the diamine. Can be carried out in substantially the same manner as the synthesis of polyamide.

The Mw of the poly (thio) ester as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

(3) Production of (meth) acrylic acid copolymer

The (meth) acrylic acid copolymer which is an example of the specific polymer in the present invention can be obtained by addition polymerization of a mixture of a polymerizable unsaturated compound containing (meth) acrylic acid and the compound (A).

In this case, as the unsaturated compound, only the (meth) acrylic acid and the compound (A) may be used, and besides the (meth) acrylic acid and the compound (A), other polymerizable unsaturated compounds may be used in combination. Examples of other polymerizable unsaturated compounds usable herein include conjugated dienes, aromatic vinyl compounds, (meth) acrylic acid esters,?,? -Unsaturated nitrile compounds and maleimide compounds. Specific examples of these conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, My back;

Examples of the aromatic vinyl compound include styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like;

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, (Meth) acrylic acid 4- (4-n-propylcyclohexyl) phenyl, the following formula (MA-2)

And the like;

Examples of the?,? - unsaturated nitrile compound include: acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile,? -Ethyl acrylonitrile, vinylidene cyanide,

As the maleimide compound, for example, N-cyclohexylmaleimide, N-phenylmaleimide and the like can be respectively enumerated, and at least one selected from the above can be used.

In the (meth) acrylic acid copolymer,

The content of the repeating unit derived from (meth) acrylic acid is preferably 0.1 to 80% by weight, more preferably 5 to 60% by weight;

The content of the repeating unit derived from the compound (A) is preferably from 0.1 to 15% by weight, and more preferably from 0.5 to 10% by weight.

(Meth) acrylic acid copolymer can be synthesized by using a polymerizable unsaturated compound as described above, for example, by known solution polymerization. This solution polymerization can be carried out in an organic solvent in the presence of a suitable polymerization initiator, preferably in the presence of a more suitable chain transfer agent.

Examples of the organic solvent include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, Ketones, esters and the like can be used. The use ratio of the organic solvent is preferably 120 to 600 parts by weight, more preferably 150 to 400 parts by weight, per 100 parts by weight of the total amount of the polymerizable unsaturated compounds.

Examples of the polymerization initiator include cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like. Of these, 1 More than species can be used. The proportion of the polymerization initiator to be used is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight, based on 100 parts by weight of the total of the polymerizable unsaturated compounds.

Examples of the chain transfer agent include azo compounds, thiuram compounds, phenol derivatives, allylated products, halogenated hydrocarbon compounds, vinyl ether compounds, triphenylethane, pentaphenylethane, , Thiomalic acid, 2-ethylhexyl thioglycolate, and? -Methylstyrene dimer, and the like, and at least one selected from the above can be used. The ratio of the chain transfer agent to be used is preferably 3 parts by weight or less, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable unsaturated compounds.

(Meth) acrylic acid copolymer is preferably carried out at a temperature of 50 to 100 占 폚, more preferably 60 to 90 占 폚, preferably 30 to 500 minutes, more preferably 60 to 300 minutes . ≪ / RTI >

The Mw of the (meth) acrylic acid copolymer as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

(4) Preparation of polyorganosiloxane

The polyorganosiloxane, which is an example of the specific polymer in the present invention, can be obtained by hydrolysis / condensation of a silane compound containing a compound (S), preferably in the presence of a suitable organic solvent and a catalyst.

As the silane compound, only the compound (S) may be used, or the compound (S) and other silane compounds may be used in combination. Examples of the other silane compounds that can be used herein include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3 Vinyltriethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, Phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxy Propyl methyldiethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Hexyl) ethyltriethoxysilane, and the like, and at least one selected from the above can be used.

When the compound (S) is used in combination with other silane compounds, the ratio of the compound (S) to be used is preferably 5 mol% or more, more preferably 10 mol% % Or more.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane include hydrocarbons, ketones, esters, ethers, and alcohols, and at least one selected from the above can be used. Specific examples of these organic solvents include hydrocarbon, ketone, ester, ether or alcohol in the solvent which can be used in the synthesis of the compound (C). As the organic solvent, a non-water-soluble organic solvent is preferably used. The use ratio of the organic solvent is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound.

As the catalyst, for example, an acid, a base, an organic base, a titanium compound, a zirconium compound and the like can be used. Of these, it is preferable to use a base.

Examples of the base include an organic base and a basic alkali metal compound. Specific examples thereof include organic bases such as primary amine and secondary amine such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, it is preferable to use triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or tetramethylammonium hydroxide. Examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

The use ratio of the catalyst is preferably 0.01 to 5 mol, more preferably 0.05 to 3 mol, per 1 mol of the total amount of the silane compound used as the raw material.

The amount of water used in synthesizing the polyorganosiloxane is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the total amount of the silane compound used as the raw material.

The synthesis reaction of the polyorganosiloxane is preferably carried out at a reaction temperature of 0 to 200 캜, more preferably 10 to 150 캜, preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours All.

The Mw of the polyorganosiloxane as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

[When a specific polymer has a pretilt angle-expressing group or photo-orienting group]

The specific polymer in the present invention can be synthesized as described above.

Next, the case where the polymer obtained in the present invention has a pretilt angular expression group or photo aligning group will be described.

The pretilt angular expressing group is a group having a property of aligning liquid crystal molecules to give a pretilt angle, and is, for example, a linear alkyl group having 4 to 30 carbon atoms (provided that it is contained in the following formula (A-1) , A straight chain fluoroalkyl group having 4 to 30 carbon atoms, a group having a steroid structure, a group represented by the following formula (A-1), and the like:

(In the formula (A-1), a is 0 or 1, b is an integer of 0 to 2, provided that a and b are not 0 at the same time, c is an integer of 1 to 20, Indicating a combined hand).

Specific examples of the group C _c H _{2c +1} - in the above formula (A-1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, N-hexyldecyl group, n-hexyldecyl group, n-hexyldecyl group, n-hexyldecyl group, n-hexyldecyl group, N-octadecyl group, n-nonadecyl group, and n-eicosyl group.

Specific examples of the groups represented by the above formula (A-1) include, for example, the following formulas (A-1-1-1), (A-1-1-2)

(Wherein, " n- " indicates a straight chain, and " * "

And the like.

The photo aligning group is a group having at least one of isomerization and dimerization by irradiation of light. Examples of such photo-alignment groups include groups having an azobenzene structure, groups having a cinnamic acid structure, groups having a chalcone structure, groups having a benzophenone structure, groups having a coumarin structure, and the like. Of these, it is preferable to apply a group having a cinnamic acid structure in view of high liquid crystal alignability, easy synthesis of monomers and introduction into polymers. The Shin-Nansan structure may be either a sheath type or a transformer type.

When the liquid crystal aligning agent of the present invention is used to form a liquid crystal alignment film formed by rubbing the coating film, the monomer having a pretilt angular expression group and the monomer having a photo aligning group as described above may be used As a ratio to the number of moles of the whole monomers, it is preferably used in a proportion of not more than 15 mol%, more preferably not more than 10 mol%, particularly preferably not.

When the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film (for example, applied to a VA type liquid crystal display element or the like) formed without rubbing the coating film, the above-mentioned pretilt angle- Is preferably used in a proportion of 2 mol% or more, more preferably 3 mol% to 30 mol%, and still more preferably 5 mol% to 20 mol% based on the total monomer .

When the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film formed by light irradiation of a coating film, it is preferable to use the monomer having a photo aligning group as described above in a proportion of 2 mol% or more based on the total monomer , More preferably 5 mol% or more, and still more preferably 10 mol% or more.

The specific polymer in the present invention may have both a pre-tilt angle-generating group and a photo-aligning group at the same time.

<Other components>

The liquid crystal aligning agent of the present invention contains the above-mentioned specific polymer as an essential component. The liquid crystal aligning agent of the present invention may contain other components optionally used in addition to the specific polymer.

Other components that can be used herein include, for example, a polymer other than a specific polymer, a compound having at least one epoxy group in the molecule (hereinafter also referred to as an &quot; epoxy compound &quot;), and a functional silane compound.

[Polymers other than the Specific Polymer]

Polymers other than the above specific polymers can be used for improving the solution properties and electrical properties. Such another polymer is a polymer having no bivalent group represented by the above formula (1), and examples thereof include imidized polymers of polyamic acid and polyamic acid, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, poly A polymer having no divalent group represented by the formula (1), wherein the polymer is at least one member selected from the group consisting of acetal, polystyrene and derivatives thereof, poly (styrene-phenylmaleimide) and derivatives thereof and poly (meth) .

The proportion of the polymer other than the specific polymer is preferably 50% by weight or less, more preferably 20% by weight or less based on the sum of the polymers (total of the polymers other than the specific polymer and the specific polymer; , More preferably 10 wt% or less. Particularly preferably, it does not contain a polymer other than the specific polymer.

[Epoxy Compound]

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl N, N, N ', N'-bis (N, N-diglycidylaminomethyl) cyclohexane, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N, Glycidyl-cyclohexylamine, and the like, and at least one selected from these may be used.

The proportion of these epoxy compounds to be used is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the polymers.

[Functional silane compound]

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyl triethoxysilane, 2- Glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like. Of these, At least one selected may be used.

The use ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total of the polymers.

&Lt; Preparation of liquid crystal aligning agent &

The liquid crystal aligning agent of the present invention is constituted as a solution phase composition in which a specific polymer and optionally other components optionally used are dissolved and contained in an organic solvent.

Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, Methylene-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene Diethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether (ethylene glycol diethyl ether), ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol- , Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, di Isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, and the like, and depending on the kind of the specific polymer to be used, at least one selected from the above- Can be used.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., Is in the range of 1 to 10% by weight. By setting the solid concentration in this range, it is preferable to form a liquid crystal alignment film having a suitable film thickness with good coating properties.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚.

&Lt; Formation of liquid crystal alignment film &

The liquid crystal aligning agent of the present invention can be used, for example,

The liquid crystal alignment film can be formed by passing the liquid crystal aligning agent of the present invention on the substrate to form a coating film (coating film formation step).

A liquid crystal aligning agent containing a specific polymer obtained by using a monomer having a pretilt angular expression group, preferably in a proportion of 2 mol% or more based on the total monomers, can be obtained by coating the coating film formed by the above coating film formation process as a liquid crystal alignment film , VA type liquid crystal display element or a retardation film. However, it may be used after the following liquid crystal orientation imparting step is performed on a formed coating film if desired. In other cases, the coating film formed by the coating film forming step can be applied to any type of liquid crystal display element or retardation film after the following liquid crystal aligning property imparting step is performed.

(1) Coating film formation process

When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of a system of the past system such as TN type, STN type and VA type, two substrates on which a patterned transparent conductive film is formed are paired And the liquid crystal aligning agent of the present invention is coated on each of the transparent conductive film forming surfaces to form a coated film. When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of a transverse electric field system such as IPS type or FFS type, a pair of electrodes And a counter substrate on which no electrode is formed are paired to form a coating film by applying the liquid crystal aligning agent of the present invention to the surface of the comb-like electrode and the surface of the counter substrate, respectively. When the liquid crystal aligning agent of the present invention is applied to a retardation film, the liquid crystal aligning agent of the present invention is applied to a single substrate (substrate having no electrode) to form a coated film.

When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display device, glass such as float glass and soda glass;

A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film made of SnO ₂ , or the like can be used. As the metal film, for example, a film made of a metal such as chromium can be used. The patterning of the transparent conductive film and the metal film includes, for example, a method of forming a pattern by a photo-etching method or a sputtering method after forming a transparent conductive film without a pattern, a method of forming a transparent conductive film by using a mask having a desired pattern Method, and the like.

On the other hand, when the liquid crystal aligning agent of the present invention is applied to a retardation film, it is preferable to use, as the substrate, triacetylcellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, A transparent substrate made of a synthetic resin such as acrylate, polycarbonate and the like can be suitably exemplified. Among them, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element.

In most cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to precisely control the angle with respect to the polarization axis of the polarizing film in a specific direction so as to exhibit the desired optical characteristics, and to bond the retardation film. Therefore, when a liquid crystal alignment film having a liquid crystal aligning ability in a predetermined angle direction is formed on a TAC film, a joining step of controlling the angle of the retardation film on the polarizing film can be omitted, Thereby contributing to improvement of productivity. The liquid crystal alignment film having a liquid crystal aligning ability in the direction of a predetermined angle can be formed by a photo alignment method using a liquid crystal aligning agent containing a polymer (B) having a liquid crystal aligning group having photo aligning ability.

Therefore, by using the TAC film as the substrate for forming the retardation film, the above advantages can be enjoyed, and the liquid crystal display element can be reduced in size and weight, and can be applied to a flexible display.

A functional silane compound, titanate or the like is coated on the substrate and the electrode in order to improve the adhesion between the substrate and the electrode and the coating film upon application of the liquid crystal aligning agent onto the substrate, Or may be carried out prior to the processing.

The application of the liquid crystal aligning agent onto the substrate can be preferably carried out by an appropriate application method such as an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. After the application, the coated surface can be formed by preheating (prebaking) the coating surface and then baking (postbaking). The prebaking condition is, for example, a heating time of 0.1 to 5 minutes at a heating temperature of 40 to 120 캜, and a post baking condition is, for example, a heating temperature of 120 to 300 캜, preferably 150 to 250 캜 For example 5 to 200 minutes, preferably 10 to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

(2) Liquid crystal aligning property imparting step

[Rubbing Process]

It is preferable that the specific polymer contained in the liquid crystal aligning agent of the present invention contains a monomer having a pretilt angular expression group and a monomer having a photo aligning group in a ratio of the total number of moles of these monomers to the total number of moles of the monomer, , The coating film formed by the coating film forming step (1) may be subjected to a rubbing treatment to impart a liquid crystal aligning ability to the coating film to form a liquid crystal alignment film.

In the rubbing treatment, the coating film formed by the above (1) coating film forming step is subjected to a rubbing treatment in which a cloth made of a long fiber such as nylon, rayon or cotton is wound around the coating film in a predetermined direction. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film, and a liquid crystal alignment film can be obtained.

The liquid crystal alignment film to which the liquid crystal alignment property is imparted by the rubbing treatment can be suitably applied to liquid crystal display elements or retardation films of TN type, STN type, IPS type or FFS type.

[Light irradiation treatment process]

When the specific polymer contained in the liquid crystal aligning agent of the present invention is obtained by using a monomer having a photo-aligning group at a ratio of preferably 2 mol% or more based on the total monomers, the step (1) The formed coating film can be made into a liquid crystal alignment film by applying polarized light thereto to give a liquid crystal aligning ability to the coating film.

As the light to be irradiated here, for example, ultraviolet rays including visible light having a wavelength of 150 to 800 nm, visible light, or the like can be used. Ultraviolet rays containing light having a wavelength of 200 to 400 nm are preferred. As the light source to be used, for example, 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 Hg-Xe lamp and an excimer laser can be used. The ultraviolet ray of the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with a filter, a diffraction grating, or the like.

When the light used for light irradiation is polarized (linearly polarized light or partial polarized light), it may be irradiated from an oblique direction for imparting a pretilt angle even if it is irradiated from a perpendicular direction to the coated film surface. On the other hand, in the case of irradiating non-polarized light, it is preferable that irradiation is performed in an oblique direction with respect to the coated film surface.

The irradiation dose of light is preferably 1 J / m 2 or more and less than 10,000 J / m 2, and more preferably 10 to 3,000 J / m 2.

The liquid crystal alignment film to which the liquid crystal aligning property is imparted by the light irradiation treatment can be suitably applied to liquid crystal display devices of arbitrary types according to the structure of the polymer contained in the liquid crystal aligning agent.

<Liquid crystal display element and retardation film>

The liquid crystal display element and the retardation film can be produced using the substrate having the liquid crystal alignment film formed as described above.

[Production of liquid crystal display device]

A liquid crystal display device can be manufactured as follows using a substrate on which a liquid crystal alignment film is formed as described above.

First, a liquid crystal cell having a structure in which a liquid crystal is sandwiched between gaps (cell gaps) in which a pair of substrates on which liquid crystal alignment films are formed are disposed opposite to each other is formed.

In order to constitute a liquid crystal cell, two substrates having a liquid crystal alignment film formed thereon are bonded so that the liquid crystal alignment film faces are opposed to each other by a sealing agent disposed in the periphery thereof, and a liquid crystal is formed in the cell gap partitioned by the liquid crystal alignment film face and the sealant A method for filling the injection port by filling the injection port;

For example, an ultraviolet curable sealant is disposed at a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed and the liquid crystal is arranged at a predetermined number of positions on the liquid crystal alignment film surface, And then the liquid crystal is spread over the entire surface of the liquid crystal alignment film by pressing and bonding the other substrate, and then the ultraviolet rays are irradiated to the entire surface of the substrate to cure the sealant.

In any of the above cases, when the rubbing process is performed at the time of forming the liquid crystal alignment film, the rubbing directions of the liquid crystal alignment films of the two substrates are orthogonal or antiparallel;

In the case of irradiating polarized light at the time of forming the liquid crystal alignment film, it is preferable to arrange them so that the directions in which the polarizing planes of the irradiation light are projected on two substrate surfaces are orthogonal or anti-parallel.

Then, the liquid crystal display element can be manufactured by bonding the polarizing plate to the outer surface of the liquid crystal cell in a predetermined direction.

As the sealing agent, for example, an epoxy resin containing a curing agent and an aluminum oxide sphere as a spacer can be used.

As the liquid crystal, a nematic liquid crystal or a smectic liquid crystal can be used. Of these, a nematic liquid crystal is preferable. Specific examples thereof include, for example, a cypher base liquid crystal, an agglutinative liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, Based liquid crystal, a bicyclooctane-based liquid crystal, a quartz-based liquid crystal, and the like. Examples of the liquid crystal include cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate;

Chiral agents such as those sold under the trade names of "C-15" and "CB-15" (Merck);

p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like may be added and used.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, for example, a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched by a cellulose acetate protective film, A polarizing plate and the like.

The liquid crystal display element obtained as described above can be effectively applied to various apparatuses and can be applied to various apparatuses such as a clock, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, a PDA, Telephone, various monitors, liquid crystal television, and the like.

[Retardation film]

The retardation film is obtained by preparing one substrate on which a liquid crystal alignment film is formed as described above, forming a coating film of a polymerizable liquid crystal on the substrate, and then curing the coating film of the polymerizable liquid crystal to form a liquid crystal layer can do.

The polymerizable liquid crystal is a liquid crystal compound or a liquid crystal composition which undergoes polymerization by at least one of heating and light irradiation.

Examples of such polymerizable liquid crystals include nematic liquid crystal compounds described in Non-Patent Document 1 ("UV Curable Liquid Crystal and Its Application", Liquid Crystal, Vol. 3, No. 1 (1999), pp. 34 to 42) . Cholesteric liquid crystals; Discotic liquid crystal; Or a twisted nematic alignment type liquid crystal to which a chiral agent is added. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may also be a composition containing a known polymerization initiator, a suitable solvent, and the like.

To apply the above-mentioned polymerizable liquid crystal on the formed liquid crystal alignment film, a suitable application method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an ink jet method can be employed.

Subsequently, the coating film of the polymerizable liquid crystal thus formed is subjected to treatment of at least one selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable that these treatments are performed in an overlapping manner because good orientation can be obtained.

The heating temperature of the coating film should be appropriately selected depending on the kind of the polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferable to heat to a temperature in the range of 40 to 80 占 폚. The heating time is preferably 0.5 to 5 minutes.

As the irradiation light, unpolarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light is preferably 50 to 10,000 mJ / cm 2, more preferably 100 to 5,000 mJ / cm 2.

The thickness of the liquid crystal layer to be formed is suitably set in accordance with a desired optical characteristic. For example, in the case of producing a half-wave plate in a visible light having a wavelength of 540 nm, the thickness is selected so that the retardation of the formed retardation film becomes 240 to 300 nm, and if it is a quarter- A thickness such that the retardation becomes 120 to 150 nm is selected. The thickness of the liquid crystal layer in which the objective phase difference is obtained differs depending on the optical characteristics of the polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for producing a 1/4 wavelength plate is in the range of 0.6 to 1.5 占 퐉.

The retardation film thus obtained can be suitably applied as a retardation film of a liquid crystal display element.

The liquid crystal display element to which the retardation film produced using the liquid crystal aligning agent of the present invention is applied is not limited to the driving method thereof and may be a TN system, an STN system, an IPS system, an FFS system, a VA system (VA-MVA Method, a VA-PVA method, and the like).

A liquid crystal display device generally has a structure in which a polarizing film is adhered to both surfaces of a liquid crystal cell in which liquid crystal is held between a pair of electrodes and a pair of substrates on which liquid crystal alignment films are formed. The retardation film is used by adhering a substrate-side surface to an outer surface of a polarizing film on a viewer side of a liquid crystal display element. Therefore, it is most preferable that the substrate of the retardation film is made of TAC and the substrate of the retardation film functions as a protective film of the polarizing film.

The liquid crystal display device comprising the retardation film produced using the liquid crystal aligning agent of the present invention as described above has an advantage that the excellent liquid crystal alignability is expressed stably for a long period of time.

(Example)

In the following Synthesis Examples, the synthesis was repeated with the scales described in each Synthesis Example as necessary to obtain the required amount of compound in the following Synthesis Examples.

&Lt; Synthesis of monomers having a bivalent group represented by the formula (1) &gt;

[Synthesis of Compound (C)

Synthesis Example C-1

Compound (C-1) was synthesized according to Reaction Scheme 1 below.

218.12 g of pyromellitic dianhydride, 266.2 g of L-aspartic acid and 1,000 mL of pyridine were mixed in a 2 L three-necked flask equipped with a reflux tube, stirred at 45 캜 for 2 hours, and then reacted under reflux for 4 hours. After the reaction, the solvent was removed by distillation under reduced pressure to obtain 448 g of the compound (C-1).

Synthesis Example C-2

Compound (C-2) was synthesized according to Reaction Scheme 2 below.

In a 2 L three-necked flask equipped with a reflux condenser, 218.12 g of pyromellitic dianhydride, 206.24 g of 4-aminobutyric acid and 1,000 mL of dimethylformamide were mixed and stirred at 45 캜 for 2 hours, and then reacted under reflux for 4 hours I did. After the reaction, distilled water was added to precipitate crystals, and the solid was collected by filtration. The recovered solid was recrystallized from ethanol to obtain 322 g of the compound (C-2).

[Synthesis of Compound (E)

Synthesis Example E-1

Compound (E-1) was synthesized according to Reaction Scheme 3 below.

In a 2 L three-necked flask equipped with a reflux condenser, 250.2 g of 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 anhydride, 150.22 g of 3- Pyridine were mixed, and the mixture was stirred at 45 캜 for 2 hours, and then reacted under reflux for 4 hours. After the reaction, distilled water was added to perform crystallization, and then the solid was filtered and recovered. The recovered solid was washed with ethanol and heated at 60 캜 under reduced pressure and dried to obtain 306 g of Compound (E-1).

Synthesis Example E-2

Compound (E-2) was synthesized according to Reaction Scheme 4 below.

In a 2 L three-necked flask equipped with a dropping funnel, 200 g of epichlorohydrin, 500 mL of a 2N (normality) aqueous solution of sodium hydroxide and 2.71 g of tetrabutylammonium bromide were placed. Then, a solution obtained by dissolving 306 g of the compound (E-1) obtained in the same manner as in Synthesis Example E-1 in 200 mL of tetrahydrofuran was slowly added dropwise from the dropping funnel. During the dropping, the flask was cooled in an ice bath to keep the internal temperature from exceeding 40 캜. After completion of the dropwise addition, the reaction was carried out with stirring at 80 DEG C for 8 hours. After the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. To this was added 500 mL of distilled water and the liquid was washed to separate the aqueous layer. This liquid cleaning operation was repeated to perform a total of four liquid cleaning operations. Thereafter, the organic layer was concentrated by vacuum distillation to obtain a solid crude product. This crude product was recrystallized from a mixed solvent of ethyl acetate as a good solvent and hexane as a poor solvent to obtain 210 g of a compound (E-2).

[Synthesis of Compound (A)

Synthesis Example A-1

Compound (A-1) was synthesized according to Reaction Scheme 5 below.

364 g of the compound (E-1) synthesized in the same manner as in Synthesis Example E-1, 303 g of triethylamine and 800 mL of tetrahydrofuran were placed in a 2 L three-necked flask equipped with a dropping funnel. A solution prepared by dissolving 210 g of acrylic acid chloride in 200 mL of tetrahydrofuran was slowly added dropwise from the dropping funnel. During the dropping, the flask was cooled in an ice bath to keep the internal temperature from exceeding 40 캜. After completion of dropwise addition, the reaction was carried out at room temperature for 6 hours. After the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. 500 ml of distilled water was further added thereto, and liquid separation was performed by separating the liquid layer and discarding the aqueous layer. This liquid cleaning operation was repeated to perform a total of four liquid cleaning operations. Thereafter, the solvent was removed by distillation under reduced pressure to obtain a solid crude product. This crude product was recrystallized from ethanol to obtain 338 g of the compound (A-1).

[Synthesis of Compound (S)

Synthesis Example S-1

Compound (S-1) was synthesized according to Reaction Scheme 6 below.

364 g of the compound (E-1) synthesized in the same manner as in Synthesis Example E-1 and 800 mL of acetic acid were placed in a 2 L three-necked flask equipped with a dropping funnel. 200 mL of sulfuric acid was slowly added dropwise from the dropping funnel. During the dropping, the flask was cooled in an ice bath to keep the internal temperature from exceeding 10 캜. After completion of dropwise addition, the reaction was carried out at room temperature for 6 hours. After the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. 500 ml of distilled water was further added thereto, and liquid separation was performed by separating the liquid layer and discarding the aqueous layer. This liquid cleaning operation was repeated to perform a total of four liquid cleaning operations. Thereafter, the solvent was removed by reduced pressure distillation to obtain a crude product of a liquid phase. This crude product was dissolved in ethyl acetate, purified by silica column, and the solvent was further removed to obtain 308 g of the compound (S-1a). Subsequently, a 1000 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube was charged with 262.7 g of the compound (S-1a), 400 mL of toluene and 40 μL of an isopropanol solution of chloroplatinic acid hexahydrate at a concentration of 0.2 mol / L, For about 10 minutes to carry out nitrogen substitution in the system, 145 g of dimethylmonomethoxysilane was added, and the reaction was carried out under reflux for 10 hours under nitrogen. The reaction mixture was passed through a short column of silica gel, purified with a silica column, and furthermore, the solvent was removed to obtain 85 g of the compound (S-1).

&Lt; Synthesis of Polymer &

[Synthesis of polysiloxane]

Synthesis Examples P-1 to P-3

The reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with a silane compound at a molar ratio shown in Table 1, and methyl isobutyl ketone was added thereto so that the total concentration of the silane compound became 20% by weight. In addition, triethylamine was added in an amount corresponding to 10 mol% based on the total molar amount of the silane compound, followed by mixing at room temperature. Then, deionized water in an amount corresponding to 0.2 times the weight of methyl isobutyl ketone was dropped from the dropping funnel, and the reaction was carried out at 80 DEG C for 6 hours.

After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed wastewater became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polysiloxane (P-1) -3), respectively.

[Synthesis of polyamide]

Synthesis Example P-4

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 30 mol% of 1,4-diaminobenzene, 60 mol% of 3,5-diaminobenzoic acid and 2,4-diamino- And 10 mol% of oxybenzene, and tetrahydrofuran was added thereto so that the total concentration of the diamine compound became 20% by weight. Triethylamine was added thereto in an amount corresponding to 300 mol% based on the total molar amount of the diamine compound and mixed at room temperature. Further, 100 mol% of the compound (C-2) (obtained in Synthesis Example C-2) relative to the total molar amount of the diamine compound was subjected to acid chloride chlorination with thionyl chloride, The solution dissolved in furan was slowly dropped from the dropping funnel to carry out a polymerization reaction. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 40 占 폚 for 15 hours to obtain a polyamide (P-4).

[Synthesis of polyester and polythioester]

Synthesis Examples P-5 to P-11

A diol compound, diepoxy compound or dithiol compound (compound (A)) was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser at a molar ratio shown in Table 2, % By weight of tetrahydrofuran. In addition, triethylamine was added in an amount corresponding to 300 mol% based on the total molar amount of the compound, and the mixture was mixed at room temperature. A solution obtained by dissolving a dicarboxylic compound having a molar ratio shown in Table 2 in thionyl chloride chloride in tetrahydrofuran at a concentration of 20% by weight was slowly dropped from a dropping funnel to carry out a polymerization reaction. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. (P-5) to (P-9) and (P-11) and a polythioester (P-10) were obtained by drying the precipitate collected by washing with methanol and drying at 40 ° C for 15 hours under reduced pressure. .

The abbreviations of the compounds in Table 2 have the following meanings respectively.

HY-1: Hydroquinone

HY-2: 3,5-dihydroxybenzoic acid

HY-3: 3,6-dihydroxy-cholestane

HY-4: 3,5-dihydroxybenzoic acid-3-cholestanyl

SH-1: benzene-1,4-dithiol

CA-1: 1,4-Dicarboxybenzene

CA-2: 1,3-Dicarboxybenzene

CA-3: 1,3-Dicarboxy-5-n-octadecaneoxybenzene

[Synthesis of methacrylic acid copolymer]

Synthesis Examples P-12 and P-13

A polymerizable unsaturated compound was added in a molar ratio shown in Table 3 to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and diethylene glycol ethyl methyl ether And dissolved. To this solution, 3 mol% of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator with respect to the total number of moles of the polymerizable unsaturated compound and? -Methylstyrene dimer as a chain transfer agent were added to the polymerization initiator 0.5 times the weight of the weight. Subsequently, the reaction system was bubbled in a stream of nitrogen for 10 minutes to carry out nitrogen substitution in the system, followed by polymerization reaction at 70 DEG C for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The collected precipitates were washed with methanol and then dried under reduced pressure at 40 占 폚 for 15 hours to obtain (meth) acrylic acid copolymers (P-12) and (P-13).

The abbreviations of the compounds in Table 3 have the following meanings respectively.

MA-1: Methacrylic acid 4- (4-n-propylcyclohexyl) phenyl

MA-2: Compound represented by the formula MA-2

[Synthesis of polyamic acid]

Synthesis Example P-14

13.179 g of pyromellitic acid dianhydride as tetracarboxylic dianhydride, 11.835 g of 1,2,3,4-cyclobutanoic acid dianhydride, 23.478 g of 4,4'-diaminodiphenylmethane as a diamine, and 23.478 g of 3,6-bis (4-aminobenzoyloxy) cholestane was dissolved in 200 g of N-methyl-2-pyrrolidone, and the reaction was carried out at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The collected precipitate was washed with methanol and then dried under reduced pressure at 40 DEG C for 15 hours to obtain 48.5 g of polyamic acid (P-14).

[Synthesis of imidized polymer]

In the following synthesis examples, the imidization rate of the imidized polymer was measured as follows.

The imidized polymer thus obtained was dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidation rate was obtained using the following equation (1): &lt; EMI ID =

Imidization ratio (%) = (1-A ¹ / A ² × α) × 100 (1)

(In the formula (1), A ¹ is the peak area derived from the proton of the NH group near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and? Is the peak area derived from the proton The ratio of the number of other protons to one proton in the NH group).

Synthesis Example P-15

3.53 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 24.72 g of 1,2,3,4-cyclobutanoic dianhydride and 2,4,6,8-tetracarboxy bicyclo 3.93 g of [3.3.0] octane-2: 4,6: 8-2 anhydride, 16.70 g of 1,4-diaminobenzene as a diamine,

Was dissolved in 200 g of N-methyl-2-pyrrolidone, and the reaction was carried out at room temperature for 6 hours to obtain a polyamic acid solution.

Next, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 37.39 g of pyridine and 80.43 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 90 DEG C for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The collected precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 47.1 g of an imidation polymer (P-15) having an imidization ratio of 94%.

Synthesis Example P-16

25.895 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 12.079 g of 3- (3,5-diaminobenzoyloxy) cholestane as diamine, 4.997 g of 1,4-diaminobenzene And 7.030 g of 2,5-diaminobenzoic acid were dissolved in 200 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours to obtain a polyamic acid solution.

Next, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 18.27 g of pyridine and 23.59 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 6 hours. The resulting reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 49.1 g of an imidized polymer (P-16) having an imidization rate of 96%.

&Lt; Preparation and evaluation of liquid crystal aligning agent &gt;

[Application example to TN type liquid crystal display element]

Example TN-1

(1) Preparation of liquid crystal aligning agent

Polysiloxane (P-1) obtained in Synthesis Example P-1 as a polymer was dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) Mass ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. This solution was sufficiently stirred, and then filtered through a filter having a pore diameter of 0.2 mu m to prepare a liquid crystal aligning agent.

(2) Evaluation of printability

The liquid crystal aligning agent prepared in "(1) Preparation of liquid crystal aligning agent" was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) (Pre-baked) on a hot plate at 80 占 폚 for 1 minute to remove the solvent and then heated on a hot plate at 200 占 폚 for 10 minutes (post baking) to form a coating film having an average film thickness of 600 占. The coating film was observed with a microscope having a magnification of 20 times to examine whether there was uneven printing or pinholes. As a result, neither printing unevenness nor pinholes were observed, and the printability was "good".

(3) Production of TN type liquid crystal cell

The liquid crystal aligning agent prepared in "(1) Preparation of liquid crystal aligning agent" was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) (Pre-baked) on a hot plate at 80 占 폚 for 1 minute to remove the solvent and then heated on a hot plate at 200 占 폚 for 10 minutes (post baking) to form a coating film having an average film thickness of 600 占. The coating film was subjected to a rubbing treatment with a rubbing machine having a roll around which a rayon spring was wound at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair pressing indentation length of 0.4 mm to give a liquid crystal aligning ability . Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then the substrate was dried in a 100 占 폚 clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film.

The above operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Next, after applying an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 占 퐉 to the outer edge of the surface having one liquid crystal alignment film among the pair of substrates, a pair of substrates was laminated on the liquid crystal alignment film surface So as to cure the adhesive. Subsequently, a nematic liquid crystal (MLC-6221, manufactured by Merck Ltd.) was filled between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection port was sealed with an acrylic light-curable adhesive to produce a TN type liquid crystal cell.

The above method was repeated to produce three TN liquid crystal cells in total, and one was provided for the evaluation of the liquid crystal orientation property, the evaluation of the pretilt angle stability and the evaluation of the heat resistance described below.

(4) Evaluation of TN type liquid crystal cell

I) Evaluation of liquid crystal orientation

With respect to the liquid crystal cell prepared above, the presence or absence of an abnormal domain when a voltage of 5 V was turned on and off under Cross Nicol was observed by a microscope at a magnification of 100 times and when the abnormal domain was not observed, Quot ;, and the case where the abnormal domain was not observed was evaluated as &quot; possible &quot; and the case where the abnormal domain was observed at the magnification of 50 times was evaluated as &quot; The liquid crystal orientation of the cell was &quot; good &quot;.

Ii) Evaluation of Pretilt Angle Stability

For the liquid crystal cell prepared above, the angle of inclination of the liquid crystal molecules from the substrate surface was measured by the crystal rotation method using He-Ne laser light, and this value was regarded as an initial pretilt angle? _IN . The crystal rotation method is disclosed in Non-Patent Document 2 (TJ Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)) and Non-Patent Document 3 (F. Nakano et al., JPN.J.Appl.Phys.vol.19 , p2013 (1980)).

An AC voltage of 5 V was applied to the liquid crystal cell after the pre-tilt (? _IN ) was measured for 100 hours as described above. Thereafter, the pretilt angle was again measured by the same method as described above, and this value was defined as the pretilt angle? _AF after voltage application.

These measured values were substituted into the following equation (2), and the amount of change (?? (°)) of the pretilt angle before and after voltage application was obtained.

?? = |? _AF- ? _IN (2)

When the value Δθ was less than 0.05 °, the pretilt angle stability was evaluated as "good", when the angle was less than 0.05 ° and less than 0.2 °, "possible" and when it was 0.2 ° or more, "poor" Was 1%, and the pretilt angle stability was &quot; good &quot;.

Iii) Evaluation of heat resistance

A voltage of 5 V was applied to the liquid crystal cell prepared above in an application time of 60 microseconds and a span of 167 milliseconds and then the voltage maintenance ratio (initial voltage maintenance ratio (VHR _BF )) after 167 milliseconds VHR-1 &quot; manufactured by Toyotecnica, and it was found to be 99.4%.

After the VHR _BF measurement, the liquid crystal display element was placed in an oven at 100 캜, and thermal stress was applied for 1,000 hours. Thereafter, the liquid crystal display element was allowed to stand at room temperature and cooled to room temperature. Thereafter, the voltage holding ratio (VHR _AF ) after thermal stress application was measured under the same conditions as the measurement of the initial voltage holding ratio.

Then, the rate of change (? VHR (%)) of the voltage holding ratio before and after the application of the thermal stress was determined by the following equation (3).

VHR (%) = ((VHR _BF - VHR _AF ) / VHR _BF ) 100 (3)

The heat resistance of the liquid crystal cell was evaluated as &quot; good &quot; when the change rate was less than 4% and the heat resistance was evaluated as &quot; Respectively.

Examples TN-2 to TN-8 and Comparative Examples TN-1 to TN-4

A liquid crystal aligning agent was prepared and evaluated in the same manner as in Example TN-1 except that the kind of the polymer used in the preparation of the liquid crystal aligning agent was changed as shown in Table 4 in the above Example TN-1.

The evaluation results are shown in Table 4.

In the comparative examples TN-2 and TN-3, printing unevenness was observed in the evaluation of the printability, so the printability was determined as &quot; bad &quot;.

[Application example to VA type liquid crystal display element]

Example VA-1

(1) Preparation of liquid crystal aligning agent

The polyester (P-8) obtained in Synthesis Example P-8 as a polymer was dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (Mass ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. This solution was sufficiently stirred, and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent.

(2) Evaluation of printability

The printability was examined in the same manner as in &quot; (2) evaluation of printability &quot; in the above Example TN-1 using the liquid crystal aligning agent prepared above. As a result, both print unevenness and pinholes were not observed, Good &quot;.

(3) Production of VA type liquid crystal cell

The liquid crystal aligning agent prepared above was coated on a transparent electrode surface of a glass substrate (1 mm thick) having a transparent electrode made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nihon Sha Sein Insights Co., Ltd.) (Post baking) for 60 minutes on a hot plate at 200 캜 to form a coating film (liquid crystal alignment film) having an average film thickness of 800 Å. This operation was repeated to obtain a pair of glass substrates (two pieces) having a liquid crystal alignment film on the transparent conductive film.

Next, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 占 퐉 was applied to the outer edge of the surface having one liquid crystal alignment film among the pair of substrates, and then the pair of substrates were superimposed on each other so as to face each other, To thereby cure the adhesive. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was charged between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to produce a VA type liquid crystal cell.

(4) Evaluation of VA type liquid crystal cell

The liquid crystal cell thus produced was evaluated for liquid crystal alignability and heat resistance in the same manner as in Example TN-1. As a result, it was found that the liquid crystal alignability was "good", the initial voltage retention was 99.0%, and the heat resistance Rate of change of voltage holding ratio) was "possible".

Example VA-2 and Comparative Example VA-1

A liquid crystal aligning agent was prepared and evaluated in the same manner as in Example VA-1 except that the kind of the polymer used in the preparation of the liquid crystal aligning agent was changed as shown in Table 5.

The evaluation results are shown in Table 5.

Further, in Comparative Example VA-1, printing unevenness was observed in evaluation of printability, so the printability was determined as &quot; poor &quot;.

[Application example to FFS type liquid crystal display element]

Example FFS-1

(1) Preparation of liquid crystal aligning agent

The acrylic acid copolymer (P-13) obtained in Synthesis Example P-13 as a polymer was dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) 50 (mass ratio)) to obtain a solution having a solid content concentration of 3.0% by weight. This solution was sufficiently stirred, and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent.

(2) Evaluation of application property

The liquid crystal aligning agent prepared above was coated on a glass substrate using a spinner, prebaked on a hot plate at 80 DEG C for 1 minute, heated (post baking) for 1 hour in an oven at 200 deg. Thereby forming a coating film having an average film thickness of 1,000 ANGSTROM. This coating film was observed under a microscope with a magnification of 20 times to examine whether the film thickness was uneven or whether pinholes were present. As a result, neither film thickness unevenness nor pinholes were observed, and the film was "good".

(3) Fabrication of FFS type liquid crystal display device

A glass substrate having two systems of electrode pairs in which a bottom electrode and a silicon nitride film having no pattern and a top electrode patterned in a comb shape in this order are stacked in this order and a pair of opposed glass substrates Respectively.

The respective systems in the two system electrode pairs are hereinafter referred to as "electrode A" and "electrode B", respectively. A schematic cross-sectional view of a pair of these electrode pairs and a schematic top view of the top electrode are shown in Fig. 1 and Fig. 2, respectively. Fig. 2 (b) is an enlarged view of a portion surrounded by a broken line in Fig. 2 (a).

The liquid crystal aligning agent prepared above was applied to one surface of the glass substrate and one surface of the opposite glass substrate using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute and then the inside of the tube was subjected to nitrogen substitution And heated in an oven at 200 DEG C for 1 hour (post baking) to form a coating film having an average film thickness of 1,000 ANGSTROM. Subsequently, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; including a bright line of 313 nm were irradiated from the normal direction of the substrate to each surface of these coating films using a Hg-Xe lamp and a Glane Taylor prism, .

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied to the periphery of the surface having one liquid crystal alignment film of the above substrate by screen printing and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, So that the directions of projection of the surface onto the substrate were parallel to each other, and the adhesive was heat-cured at 150 DEG C for 1 hour. Subsequently, a liquid crystal "MLC-6221" manufactured by Merck Ltd. was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then slowly cooled to room temperature.

Next, a polarizing plate was bonded to both outer sides of the substrate to produce an FFS type liquid crystal display element. At this time, one of the polarizing plates is adhered so that the polarizing direction thereof is parallel to the projection direction of the polarizing surface of the polarizing ultraviolet ray of the liquid crystal alignment film to the substrate surface, and the other polarizing direction is opposite to the polarizing direction of the polarizing plate And adhered directly.

The above method was repeated to produce three FFS type liquid crystal cells in total, and one was provided for the evaluation of the liquid crystal orientation property, the evaluation of the heat resistance and the evaluation of the afterimage characteristic described below.

(4) Evaluation of FFS type liquid crystal display device

I) Evaluation of liquid crystal orientation

With respect to the liquid crystal display device manufactured as described above, the presence or absence of an abnormal domain in a change in light and dark when a voltage of 5 V was turned on / off (applied / released) was observed under a microscope at a magnification of 50 times. When the abnormal domain was not observed, the liquid crystal alignability was evaluated as &quot; good &quot; and when the abnormal domain was observed, the liquid crystal alignability was evaluated as &quot; bad &quot;

Ii) Evaluation of heat resistance

As a result of evaluating the heat resistance of the liquid crystal display device manufactured as described above in the same manner as in Example TN-1, the initial voltage holding ratio was 99.2% and the heat resistance (rate of change of voltage holding ratio before and after applying heat stress) was "good".

Iii) Evaluation of afterimage characteristics

The liquid crystal display device manufactured as described above was placed under an environment of 25 캜 and 1 atmospheric pressure, and a voltage was applied to the electrode A and a synthesized voltage consisting of an AC voltage of 3.5 V and a DC voltage of 5 V was applied to the electrode A for 2 hours. Immediately thereafter, a voltage of 4 V of alternating current was applied to both the electrode A and the electrode B. Then, the time (afterimage erase time) until the difference in light transmittance between the electrodes A and B from the point in time when the voltage of 4 V of AC was started to be applied to both electrodes became visually unrecognizable was measured, It was investigated whether it corresponds to five steps.

A: Less than 20 seconds

B: 20 seconds to less than 60 seconds

C: 60 seconds to less than 100 seconds

D: Less than 100 seconds and less than 150 seconds

E: 150 seconds or more

The shorter this time is, the less the afterimage will be generated.

The afterimage evaluation time of the liquid crystal display element of this embodiment was evaluated as being in the shortest "A" rank.

[Application example to retardation film]

Example PD-1

(1) Production of retardation film

On one side of the TAC film as the substrate, the liquid crystal aligning agent prepared in Example FFS-1 was applied using a bar coater and baked in an oven at 120 deg. C for 2 minutes to form a 100 nm thick coating film. Subsequently, 100J / m &lt; 2 &gt; of polarized ultraviolet rays including a bright line of 313 nm was irradiated from the normal direction of the substrate using a Hg-Xe lamp and a Gantry prism on the surface of this coating film to form a liquid crystal alignment film.

The polymerizable liquid crystal (product name: "RMS03-013C"), which had been filtered with a filter having a pore size of 0.2 탆, was coated on the liquid crystal alignment film formed above by a bar coater and then dried in an oven set at 50 캜. Minute baking was performed to form a polymerizable liquid crystal film. Next, on the film surface of the polymerizable liquid crystal, a polymerizable liquid crystal was cured by irradiating 10,000 J / m 2 of unpolarized ultraviolet light including a bright line of 365 nm using a Hg-Xe lamp to produce a retardation film.

(2) Evaluation of retardation film

I) Liquid crystal orientation

The liquid crystal alignability of the retardation film prepared above was observed by visual observation under a cross-nicol and a polarizing microscope. When the orientation is good in the naked eye and the abnormal domain is not observed by a polarization microscope, the liquid crystal alignability is excellent;

When the abnormal domain is observed with a polarizing microscope, the alignment property is good in the naked eye, the liquid crystal alignment property is good;

When the liquid crystal orientation abnormality was visually observed, the liquid crystal alignability was determined to be defective. As a result, the liquid crystal alignability of this retardation film was evaluated as &quot; good &quot;.

Ii) Adhesion

The retardation film prepared above was cut at intervals of 1 mm with a cutter knife using an equal interval spacer having a guide to form a 10 × 10 grid pattern. Subsequently, the cellophane tape was brought into close contact with the grid pattern, and then peeled off. The cut-out portion of the grid pattern after removing the cellophane tape was visually observed. At this time, when peeling of the pattern is not confirmed at all along the cut-off line or at the crossing portion of the lattice pattern, the adhesion is "good";

When the number of grid eyes in which peeling occurred is less than 15, the adhesion is "good";

When the number of lattice peaks in which peeling occurred was 15 or more, the adhesion was evaluated as &quot; poor &quot;, and as a result, the adhesion of this retardation film was &quot; good &quot;.

a: glass substrate
b: a liquid crystal alignment film
c: Top electrode (comb structure)
d: silicon nitride film
e: bottom electrode (no pattern)
f: direction of polarizing plane of polarized ultraviolet ray

Claims (13)

A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyorganosiloxane, polyamide, poly (thio) ester and (meth) acrylic acid copolymer, wherein the polymer is represented by the following formula A liquid crystal aligning agent characterized by having a divalent group:

(In the formula (1), Q represents a tetravalent organic group, Y ¹ and Y ² each represent a divalent organic group, and "*" represents a bonding bond bonded to the polymer chain, respectively. The method according to claim 1,
Wherein the polymer is a polyorganosiloxane obtained by hydrolysis / condensation of a silane compound containing a compound represented by the following formula (S)

(Wherein Q, Y ¹ and Y ² are the same as those in the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms or a X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom; and n 1 and n 2 are each independently an integer of 1 to 3). The method according to claim 1,
Wherein the polymer is a polyamide obtained by reacting a diamine with a compound represented by the following formula (C):

(In the formula (C), Q, Y ¹ and Y ² have the same meanings as those in the formula (1), and n 3 and n 4 are each independently 1 or 2). The method according to claim 1,
Wherein the polymer is a poly (thio) ester obtained by reacting at least one member selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound with a compound represented by the following formula (C)

(In the formula (C), Q, Y ¹ and Y ² have the same meanings as those in the formula (1), and n 3 and n 4 are each independently 1 or 2). The method according to claim 1,
Wherein the polymer is a poly (thio) ester obtained by reacting a compound represented by the following formula (E) with a dicarboxylic acid:

(Wherein Q, Y ¹ and Y ² have the same meanings as in the above formula (1), and Z ¹ and Z ² each independently represent a hydroxyl group, a thiol group or an epoxy group) . The method according to claim 1,
(Meth) acrylic acid copolymer obtained by addition polymerization of a mixture of a polymerizable unsaturated compound containing (meth) acrylic acid and a compound represented by the following formula (A)

(In the formula (A), Q, Y ¹ and Y ² are the same as those in the formula (1), and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group). 7. The method according to any one of claims 1 to 6,
A liquid crystal aligning agent used for forming a liquid crystal alignment film in a retardation film of a liquid crystal display element. 7. The method according to any one of claims 1 to 6,
A liquid crystal aligning agent used for forming a liquid crystal alignment film in a liquid crystal cell of a liquid crystal display element. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 6. A retardation film of a liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to claim 7. A liquid crystal cell of a liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to claim 8. A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 7. A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 8.

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