KR101866834B1 - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

(식 (1) 중, Y¹ 및 Y²는, 각각 독립적으로, 2가의 유기기이고, Z¹ 및 Z²는, 각각 독립적으로, 3가의 유기기이고, Q는 4가의 유기기이고, 그리고 n1 및 n2는, 각각 독립적으로, 0 또는 1임).(Problem) It is intended to provide a liquid crystal aligning agent having properties exceeding that of a liquid crystal aligning agent containing a partially imidized polymer of polyamic acid while omitting the imidization step of the polymer and the subsequent solvent substitution step.
A liquid crystal aligning agent characterized by containing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride containing a compound represented by the following formula (1) with a diamine:

(Wherein, in the formula (1), Y ¹ and Y ² each independently represent a divalent organic group; Z ¹ and Z ² each independently represent a trivalent organic group; Q represents a tetravalent organic group; and and n1 and n2 are each independently 0 or 1).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal display element,

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. According to a preferred embodiment of the present invention, the liquid crystal aligning agent can be produced without the necessity of the imidization step of the polymer and the subsequent solvent substitution step.

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 a liquid crystal aligning agent containing a polymer onto a substrate. As the polymer contained in the liquid crystal aligning agent, there are known imidized polymers of polyamic acids and polyamic acids, polyamides, polyesters, polyorganosiloxanes and the like. Particularly, partially imidized polymers of polyamic acids have both solubility and electrical characteristics (Patent Document 1).

A liquid crystal aligning agent containing a partially imidized polymer of polyamic acid is usually prepared through a multistage process as described below. First, a step of reacting a tetracarboxylic acid dianhydride and a diamine in an organic solvent to synthesize a polyamic acid is carried out. Next, a dehydrating agent and a dehydration catalyst are added to a solution containing polyamic acid and heated to partially imidize the polyamic acid to obtain a partially imidized polymer. This imidation process requires a long time of about 4 to 6 hours, for example. Further, since the dehydrating agent and the dehydration catalyst remain in the reaction mixture obtained in this imidation step together with the aimed polymer, it is necessary to carry out a solvent substitution step or reprecipitation purification of the polymer in order to remove them. In addition, by blending other components as required, the desired liquid crystal aligning agent can be obtained.

Thus, in general, a liquid crystal aligning agent containing a partially imidized polymer of polyamic acid is required to be prepared for a long time and solvent replacement or reprecipitation is scheduled during the process. Therefore, Of the capacity of the battery, and the manufacturing cost is further increased. Even the process of replacing the solvent of the solution containing the polymer alone is enormous in energy and cost.

Japanese Patent Application Laid-Open No. 9-157392 Japanese Laid-Open Patent Publication No. 2010-97188

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned phenomenon, and it is an object of the present invention to provide a liquid crystal aligning device having characteristics exceeding a liquid crystal aligning agent containing a partially imidized polymer of polyamic acid while omitting the imidization step of the polymer and the subsequent solvent substitution step And to provide a liquid crystal aligning agent.

According to the present invention,

A liquid crystal aligning agent characterized by containing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride containing a compound represented by the following formula (1) with a diamine:

(In the formula (1), Y ¹ and Y ² each independently represent a divalent organic group,

Z ¹ and Z ² each independently represent a trivalent organic group,

Q is a 4-valent organic group, and

and n1 and n2 are each independently 0 or 1).

According to the present invention, there is provided a liquid crystal aligning agent having properties exceeding conventionally known liquid crystal aligning agents containing a partially imidized polymer of polyamic acid.

Since the polyamic acid which can be contained in the liquid crystal aligning agent of the present invention has an imide ring derived from the tetracarboxylic acid dianhydride as a raw material, there is no need to pass through the imidization step after the polymerization and the solvent substitution step. Since the cost for producing the tetracarboxylic acid dianhydride is small compared with the cost of the imidization process and the solvent replacement process of the polymer, the total cost for preparing the liquid crystal aligning agent is reduced.

In addition, since the polyamic acid which can be contained in the liquid crystal aligning agent of the present invention has a unique structure in which the imide ring and the arate acid unit are alternately linked in the molecule, the liquid crystal aligning agent of the present invention containing the same, It is possible to exhibit characteristics that could not be expressed, for example, a uniform coating film forming ability as much as possible.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention contains a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride containing a compound represented by the above formula (1) with a diamine.

It is preferable that n1 and n2 in the above formula (1) are all 0 or all 1s.

When n1 and n2 in the formula (1) are each 0, the compound represented by the formula (1) is obtained by reacting the tetracarboxylic acid dianhydride represented by the following formula (T-1) with a monoaminodicarboxylic acid compound, To obtain a tetracarboxylic acid compound, followed by dehydration ring closure of the tetracarboxylic acid compound.

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

In this case, the unit represented by the following formula (T) in the formula (1) is a tetravalent group derived from the tetracarboxylic acid dianhydride represented by the formula (T-1)

The unit consisting of Y ¹ -Z ¹ and the unit consisting of Y ² -Z ² is a trivalent group derived from a monoamino dicarboxylic acid compound.

(In the formula (T), Q is the same as that in the formula (1), and "*" represents a bonding hand).

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

The trivalent group derived from the monoamino dicarboxylic acid compound means a trivalent group obtained by removing the amino group and the two carboxy groups from the monoamino dicarboxylic acid compound.

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 2 (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.

Examples of the monoaminodicarboxylic acid compound include, for example, aspartic acid, glutamic acid, 2-aminoadipic acid, carbocysteine, 2,3-dicarboxy aniline, 3,4-dicarboxy aniline, Amino 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-dicarboxylic naphthalene, Amino-2,3-dicarboxy naphthalene, 7-amino-2,3-dicarboxy naphthalene and 8-amino-2,3-dicarboxy naphthalene, and at least one selected from the group consisting of .

The reaction of the tetracarboxylic acid dianhydride represented by the formula (T-1) with the monoaminodicarboxylic acid compound can be carried out by heating 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, in terms of the ratio of the monoaminodicarboxylic acid compound to 1 mole of the tetracarboxylic acid dianhydride, More preferably 1.8 to 2.5 mol.

As the solvent used in this reaction, an organic solvent is preferable, and for example, a non-polar solvent such as a polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, .

Specific examples of these organic solvents include, but are not limited to, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, Butyrolactone, tetramethylurea, hexamethylphosphotriamide, 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. Or more.

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 more preferably 100 to 2,000 parts by weight, based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and the monoamino dicarboxylic acid compound. It is more preferable to divide into parts.

The reaction of the tetracarboxylic acid dianhydride with the monoaminodicarboxylic acid compound is preferably carried out at a temperature of 50 to 300 캜, more preferably 80 to 200 캜, preferably 0.1 to 10 hours, For 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 above temperature and reaction time.

By reacting the tetracarboxylic acid dianhydride and the monoaminodicarboxylic acid compound as described above, a tetracarboxylic acid compound as an intermediate compound is obtained. Subsequently, the tetracarboxylic acid compound is subject to dehydration ring-closure reaction to obtain a compound wherein n1 and n2 are each 0 in the above formula (1).

The dehydration ring closure reaction of the tetracarboxylic acid compound can be carried out, for example, by a method of bringing the tetracarboxylic acid compound into contact with a dehydrating agent. This contact may be carried out in a solvent or in the coexistence of a dehydration ring-closing catalyst.

As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.1 to 100 moles, more preferably 2 to 100 moles, per 1 mole of the tetracarboxylic acid compound.

As the solvent used in the dehydration ring-closing reaction, the solvent exemplified above as the solvent used in the reaction of the tetracarboxylic acid dianhydride represented by the formula (T-1) with the monoaminodicarboxylic acid compound can be preferably used have.

The use ratio of the solvent is preferably 500 parts by weight or less, more preferably 100 parts by weight or less, based on 100 parts by weight of the total amount of the tetracarboxylic acid compound and the dehydrating agent. In the most preferred embodiment of the present invention, a solvent is not used when contacting the tetracarboxylic acid compound with the dehydrating agent.

As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The use ratio of the dehydration ring-closing catalyst is preferably 500 moles or less, more preferably 100 moles or less, per 1 mole of the dehydrating agent. In the most preferred embodiment of the present invention, the dehydration ring-closing catalyst is not used when contacting the tetracarboxylic acid compound with the dehydrating agent.

The contact between the tetracarboxylic acid compound and the dehydrating agent is preferably carried out at a temperature of 50 to 300 캜, more preferably 80 to 200 캜, preferably 0.1 to 20 hours, more preferably 0.1 to 10 hours .

As described above, a compound in which n1 and n2 are each 0 in the formula (1) can be obtained.

When n1 and n2 in the formula (1) are each 1, the compound represented by the formula (1) is obtained by reacting the tetracarboxylic acid dianhydride represented by the formula (T-1) with an aminoalcohol compound to obtain an intermediate compound To obtain a hydroxy compound, and then further reacting the dihydroxy compound with a halide of a tricarboxylic acid monoanhydride.

In this case, the unit represented by the formula (T) in the formula (1) is a tetravalent group derived from the tetracarboxylic dianhydride represented by the formula (T-1)

Y ¹ and Y ² are a divalent group derived from an aminoalcohol compound, and

Z ¹ and Z ² are a trivalent group derived from a halide of a tricarboxylic acid monoanhydride. The tetravalent group derived from the tetracarboxylic dianhydride represented by the formula (T-1) means a tetravalent group obtained by removing two oxygen atoms constituting the ring from the tetracarboxylic dianhydride;

The divalent group derived from an aminoalcohol compound means a divalent group obtained by removing an amino group and a hydroxyl group from the aminoalcohol compound; And

Examples of the trivalent group derived from the halide of the tricarboxylic acid monohydrate include an acid anhydride group (group -C (= O) -OC (= O) -) and group -COOX , And X is a halogen atom).

The tetracarboxylic acid dianhydride represented by the formula (T-1) is the same as described above when n1 and n2 in the formula (1) are each 0.

Examples of the aminoalcohol compound include aminomethanol, 2-aminoethanol, 1-amino-2-propanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, -Hydroxyaniline, 4-hydroxyaniline and the like, and it is preferable to use at least one selected from these.

Examples of the halide of the tricarboxylic acid monoanhydride include a halide of 4-haloformylphthalic anhydride, propane-1,2,3-tricarboxylic acid monoanhydride, a butane-1,2,3-tricarboxylic acid A halide of a monoanhydride, a halide of a butane-1,2,4-tricarboxylic acid monoanhydride, a halide of a pentane-1,2,3-tricarboxylic acid monoanhydride, a pentane-1,2,4-tricarbon A halide of an acid anhydride, a halide of a pentane-1,2,5-tricarboxylic acid monoanhydride, and a halide of a cyclohexane-1,2,4-tricarboxylic acid monoanhydride. Of these, It is preferable to use at least one selected. Examples of the halogen atom contained in the halide of the tricarboxylic acid monoanhydride include a chlorine atom, a bromine atom and an iodine atom, among which a chlorine atom is preferable.

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

The ratio of the two compounds in this reaction is preferably 1 to 5 moles, more preferably 1 to 3 moles, in terms of the ratio of the aminoalcohol compound to 1 mole of the tetracarboxylic acid dianhydride.

As the solvent used in this reaction, the solvent exemplified above as the solvent used in the reaction of the tetracarboxylic acid dianhydride represented by the formula (T-1) with the monoaminodicarboxylic acid compound can be 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 the tetracarboxylic acid dianhydride and the aminoalcohol compound Is more preferable.

The reaction of the tetracarboxylic acid dianhydride with the aminoalcohol compound 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 ~ 20 hours. Optionally, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the range of the above temperature and reaction time.

By the reaction of the tetracarboxylic dianhydride and the aminoalcohol compound as described above, a dihydroxy compound as an intermediate compound is obtained. Subsequently, by reacting the dihydroxy compound with a halide of a tricarboxylic acid monoanhydride, a compound in which n1 and n2 are each 1 in the formula (1) can be obtained. This reaction can be carried out by heating these compounds, preferably in a suitable solvent.

The ratio of the two compounds in this reaction is preferably 2 to 5 moles, more preferably 2 to 3 moles, of the halide of the tricarboxylic acid monohydride relative to 1 mole of the dihydroxy compound .

As the solvent used in this reaction, the solvent exemplified above as the solvent used in the reaction of the tetracarboxylic acid dianhydride represented by the formula (T-1) with the monoaminodicarboxylic acid compound can be 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, per 100 parts by weight of the total of the dihydroxy compound and the halide of the tricarboxylic acid monohydrate.

The reaction of the dihydroxy compound with a halide of a tricarboxylic acid monohydride is preferably carried out at a temperature of -50 to 150 캜, more preferably 0 to 100 캜, preferably 0.1 to 30 hours, Preferably 0.1 to 15 hours. Optionally, the reaction may be carried out while raising the reaction temperature stepwise or continuously.

Thus, a compound in which n1 and n2 are each 1 in the above formula (1) can be obtained.

The liquid crystal aligning agent of the present invention preferably contains a polyamic acid obtained by reacting a diamine with a tetracarboxylic acid dianhydride containing the compound represented by the formula (1) obtained as described above.

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid, only the compound represented by the formula (1) may be used, or the compound represented by the formula (1) may be used in combination with other tetracarboxylic acid dianhydrides good. Examples of other tetracarboxylic acid dianhydrides that can be used in combination here include tetracarboxylic dianhydrides represented by the above formula (T-1), particularly preferably 1,2,3,4- Cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo- 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2, 3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro- 3 '- (tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 5,8,10-tetraon, bicyclo [3.3.0] octane-2,4,6,8-tetracarbon 2 is at least one member selected from the anhydride, and pyromellitic acid group consisting of a dianhydride.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of the present invention is a tetracarboxylic acid dianhydride which contains the compound represented by the formula (1) in an amount of 20 mol% or more based on the total amount of the tetracarboxylic acid dianhydride , More preferably at least 50 mol%, particularly preferably only the compound represented by the above formula (1).

Examples of the diamine used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of the present invention include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4 Bis (4-aminophenoxy) phenyl] propane, 2, 3'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, dodecaneoxy-2,4-diaminobenzene, Decanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, 3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 5-diaminobenzoic acid cholesteryl, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane and the like, and diamines described in Patent Document 2 (Japanese Patent Laid-Open Publication No. 2010-97188) Is preferably used.

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used for the synthesis reaction of the polyamic acid is such that the ratio of the acid anhydride group of the tetracarboxylic dianhydride to the equivalent of the amino group contained in the diamine compound is 0.2 to 2 equivalents , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in a suitable solvent under a temperature condition of preferably -20 to 150 占 폚, more preferably 0 to 100 占 폚, preferably 0.5 to 24 hours, 2 to 10 hours. Examples of the solvent to be used herein include N-methyl-2-pyrrolidone and? -Butyrolactone, and it is preferable to use at least one selected from these solvents.

The weight average molecular weight (Mw) of the polyamic acid in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. The ratio (Mw / Mn) of the Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. Since the Mw and the Mw / Mn of the polyamic acid are in the above-mentioned ranges, the liquid crystal aligning agent containing the liquid crystal aligning agent is preferable because both the stability as a composition and the good liquid crystal alignability of the formed liquid crystal alignment film can be satisfied.

The liquid crystal aligning agent of the present invention preferably contains the polyamic acid obtained as described above, but may contain other components as long as the effects of the present invention are not attenuated. Other components that can be used here include, for example, an epoxy compound, a functional silane compound, and the like. The epoxy compound is preferably a compound having two or more epoxy groups in the molecule. The functional silane compound is preferably a silane compound having an epoxy group or an oligomer thereof.

The liquid crystal aligning agent of the present invention is preferably a solution-like composition obtained by dissolving the above-mentioned polyamic acid and optionally other components in a suitable solvent. Examples of the solvent used in the liquid crystal aligning agent include N-methyl-2-pyrrolidone,? -Butyrolactone, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, , Propylene glycol monomethyl ether, ethyl cellosolve, 2,3-pentanedione, 1,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane and the like. . ≪ / RTI >

The solid concentration of the liquid crystal aligning agent (the ratio of the total weight of the components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is preferably in the range of 1 to 10 wt%.

The liquid crystal display element of the present invention is constituted by two pairs of substrates on which a liquid crystal alignment film is formed and a liquid crystal arranged in a gap in which the pair of substrates are arranged close to each other so as to face the liquid crystal alignment film face. Here, the pair of substrates has at least one pair of electrodes. The electrode pair may be an electrode formed on each of the two substrates and generating an electric field in a direction perpendicular to the substrate surface; or

Or may be formed on one of the substrates to generate an electric field in the horizontal direction with respect to the substrate surface.

In order to form a liquid crystal alignment film on a substrate, the liquid crystal aligning agent of the present invention may be coated on the substrate by a known method, followed by heating to form a coating film. The formed coating film may be subjected to rubbing treatment known in the art, if necessary.

Since the polyamic acid contained in the liquid crystal aligning agent of the present invention has a unique and homogeneous structure in which the imide ring and the arnamic acid unit are alternately linked in the molecule, the liquid crystal aligning agent of the present invention containing the same has a very uniform film- Can be expressed. Therefore, the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention is excellent in in-plane uniformity.

The liquid crystal display element of the present invention including the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention is excellent in uniformity of liquid crystal alignment, electrical characteristics, afterimage characteristics, and the like.

[Example]

<Synthesis of tetracarboxylic acid dianhydride represented by formula (1)> [

Synthesis Example A-1

Compound (A-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 placed in a 2 L three-necked flask equipped with a reflux condenser, and the mixture was 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 (A-1a).

Subsequently, 448 g of the compound (A-1a) obtained above and 700 g of acetic anhydride were added to a 1 L three-necked flask equipped with a reflux tube, mixed and reacted under reflux for 4 hours and then subjected to vacuum distillation to remove acetic anhydride To obtain 400 g of the aimed compound (A-1).

Synthesis Example A-2

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

218.12 g of pyromellitic dianhydride, 362.3 g of 3,4-dicarboxy aniline and 1,000 mL of dimethylformamide were placed in a 2 L three-necked flask equipped with a reflux condenser and stirred at 45 캜 for 2 hours, followed by stirring for 4 hours The reaction was carried out under reflux. After the reaction, the solvent was removed by distillation under reduced pressure to obtain 540 g of the compound (A-2a).

Subsequently, 540 g of the compound (A-2a) obtained above and 700 g of acetic anhydride were added to a 1 L three-necked flask equipped with a reflux tube, mixed and reacted under reflux for 4 hours and then subjected to vacuum distillation to remove acetic anhydride To obtain 495 g of a target compound (A-2).

Synthesis Example A-3

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

224.17 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 122.16 g of 2-aminoethanol and 1,000 mL of dimethylformamide were placed in a 2 L three-necked flask equipped with a reflux condenser and stirred at 45 ° C for 2 hours And then the reaction was carried out under reflux for 4 hours. After the reaction, the solvent was removed by distillation under reduced pressure to obtain 308 g of the compound (A-3a).

Subsequently, 308 g of the compound (A-3a) obtained above and 400 mL of tetrahydrofuran (THF) were dissolved in a 2 L three-necked flask equipped with a dropping funnel, and 400 g of triethylamine was further added thereto. A solution prepared by dissolving 421.14 g of 4-chloroformylphthalic anhydride in 800 mL of tetrahydrofuran under ice-cooling (ice cooling) was slowly added dropwise from the dropping funnel. After completion of dropwise addition, the reaction was carried out by stirring at room temperature for 3 hours. After the reaction, the triethylamine hydrochloride which was generated as a by-product from the reaction mixture was separated by filtration. Further, THF was removed by distillation under reduced pressure, and 1,000 mL of chloroform was added to obtain a solution. The resulting solution was washed with water, and the organic layer was dried over magnesium sulfate, and then chloroform was removed by distillation under reduced pressure to obtain a solid crude product. This crude product was recrystallized from acetic anhydride to obtain 610 g of the compound (A-3).

<Synthesis of polyamic acid>

Synthesis Example P-1

16.639 g of the compound (A-1) obtained in the above Synthesis Example A-1 as tetracarboxylic acid dianhydride, 7.842 g of 4,4'-diaminodiphenylmethane as a diamine, and 3,6-bis (4-aminobenzoyloxy) 0.519 g of cholestane was dissolved in 100 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 recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 24.2 g of polyamic acid (P-1).

Synthesis Example P-2

17.762 g of the compound (A-2) obtained in the above Synthesis Example A-2 as tetracarboxylic acid dianhydride, 6.789 g of 4,4'-diaminodiphenylmethane as a diamine, and 3,6-bis (4-aminobenzoyloxy) 0.449 g of cholestane was dissolved in 100 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 recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 24.6 g of polyamic acid (P-2).

Synthesis Example P-3

19.018 g of the compound (A-3) obtained in Synthesis Example A-3 as tetracarboxylic acid dianhydride and 5.611 g of 4,4'-diaminodiphenylmethane as a diamine were mixed together and 3,6-bis (4-aminobenzoyloxy) 0.371 g of cholestane was dissolved in 100 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 recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 24.3 g of polyamic acid (P-3).

Synthesis Example P-4

17.055 g of the compound (A-1) obtained in Synthesis Example A-1 as tetracarboxylic acid dianhydride, 3.597 g of p-phenylenediamine as a diamine and 4.348 g of 3- (3,5-diaminobenzoyloxy) Was dissolved in 100 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 recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 24.5 g of polyamic acid (P-4).

Comparative Synthesis Example rp-1

12.822 g of pyromellitic dianhydride as tetracarboxylic dianhydride, 11.422 g of 4,4'-diaminodiphenylmethane as diamine and 0.756 g of 3,6-bis (4-aminobenzoyloxy) cholestane were dissolved in N-methyl- Dissolved in 100 g of 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 recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 24.1 g of polyamic acid (rp-1).

Comparative Synthesis Example rp-2

12.822 g of pyromellitic dianhydride as tetracarboxylic dianhydride, 11.422 g of 4,4'-diaminodiphenylmethane as diamine and 0.756 g of 3,6-bis (4-aminobenzoyloxy) cholestane were dissolved in N-methyl- Dissolved in 100 g of 2-pyrrolidone, and the reaction was carried out at room temperature for 6 hours. Next, 125 g of NMP was added to the obtained polyamic acid solution, and 4.65 g of pyridine and 6 g of acetic anhydride were added, followed by dehydration ring closure reaction at 80 占 폚 for 3 hours. The reaction mixture obtained was then 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 23.8 g of polyimide (rp-2) having an imidization rate of 50%.

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

Example 1

(1) Preparation of liquid crystal aligning agent

The polyamic acid (P-1) obtained in Synthesis Example P-1 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) ) To prepare a solution having a solid concentration of 6.5% by weight. This solution was sufficiently stirred, and then filtered through a filter having a pore diameter of 0.2 탆 to prepare a liquid crystal aligning agent.

(2) Evaluation of printability

The liquid crystal aligning agent prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) After the solvent was removed by heating (prebaking), the film was heated on a hot plate at 200 ° C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 Å. The coating film was observed with a microscope having a magnification of 20 times to examine whether the printing was uneven or pinholes. As a result, unevenness in printing and pinholes were not observed, and the printing properties were good.

(3) Evaluation of Film Thickness Uniformity of Coating Film

With respect to the coating film formed above, the film thickness at the central portion of the substrate and the film thickness at a position near the center of 15 mm from the outer end of the substrate were measured using a contact-type film deposition apparatus (manufactured by KLA Tencor Corporation) . The film thickness uniformity was evaluated as &quot; good &quot; when the film thickness difference at the two positions was 20 angstroms or less and the film thickness uniformity was evaluated as &quot; defective &quot; when the film thickness difference exceeded 20 angstroms. did.

(4) Preparation of TN type liquid crystal cell

The liquid crystal aligning agent prepared above was applied to a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengattsu Co., Ltd.) and heated on a hot plate at 80 캜 for 1 minute (Prebaked) to remove the solvent, and then heated (post baking) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. The coating film was rubbed with a rubbing machine having a roll covered with a rayon cloth 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 , And the adhesive was cured. Subsequently, a nematic liquid crystal (MLC-6221 manufactured by Merck Ltd.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection port was sealed with an acrylic-based photo-curable adhesive to produce a TN type liquid crystal cell .

(5) Evaluation of liquid crystal cell

I) Evaluation of liquid crystal orientation

The liquid crystal cell prepared above was observed under a microscope for the presence of an abnormal domain when the voltage was turned on and off under Cross Nicol and when the abnormal domain was not observed, the liquid crystal alignability was evaluated as &quot; good & The case where the domain was observed was evaluated as &quot; poor &quot; in the liquid crystal alignment property. As a result, the liquid crystal alignability of this liquid crystal cell was found to be &quot; good &quot;.

Ii) Evaluation of Voltage Conservation Rate

A voltage of 5 V was applied to the liquid crystal display device manufactured in the above manner at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release was measured. As the measuring apparatus, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

As a result, the voltage holding ratio of this liquid crystal display element was 98.8%.

Iii) Evaluation of afterimage characteristics

A voltage of 17 V DC was applied to the liquid crystal display device manufactured above at an environmental temperature of 100 캜 for 20 hours, and the voltage (residual DC voltage) remaining in the liquid crystal cell immediately after the DC voltage was cut off was irradiated with backlight While it was obtained by the flicker erase method. The value of the residual DC voltage of this liquid crystal display element was 20 mV.

It is empirically apparent that when the value of the residual DC voltage obtained by the flicker elimination method while irradiating the backlight is 100 mV or less, the afterimage characteristic is good.

Examples 2 and 3 and Comparative Examples 1 and 2

The polyamic acids P-2 and P-3 obtained in the above Synthesis Example and the polyamic acids rp-1 and rp-2 obtained in Comparative Synthesis Example were used in place of the polyamic acid (P-1) The liquid crystal aligning agent was adjusted and evaluated in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 1.

Example 4

(1) Preparation of liquid crystal aligning agent

The polyamic acid (P-4) obtained in Synthesis Example P-4 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) ) To prepare a solution having a solid 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

Using the liquid crystal aligning agent prepared above, a coating film was formed in the same manner as in &quot; (2) evaluation of printability &quot; in Example 1, and the printability of the liquid crystal aligning agent was examined. As a result, No print irregularity and no pinholes were observed, and the printability was good.

(3) Evaluation of Film Thickness Uniformity of Coating Film

The coating film formed above was evaluated for film thickness uniformity in the same manner as in "(3) Evaluation of film thickness uniformity of coating film" in Example 1, and as a result, the film thickness uniformity of this coating film was It was good.

(4) Production of Vertical Liquid Crystal Cell

The liquid crystal aligning agent prepared above was applied to 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 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 that the liquid crystal alignment film surface was opposed to each other, And the adhesive was cured. 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 port was sealed with an acrylic photo-curable adhesive to manufacture a vertical liquid crystal cell.

(5) Evaluation of liquid crystal cell

i) Evaluation of Liquid Crystal Orientation

The liquid crystal cell thus prepared was evaluated for liquid crystal alignability in the same manner as in &quot; i) Evaluation of liquid crystal alignability &quot; in Example 1. As a result, no abnormal domains were observed by microscopic observation and the liquid crystal alignability was "good" .

Ii) Evaluation of Voltage Conservation Rate

With respect to the liquid crystal cell prepared above, the voltage holding ratio was measured in the same manner as in &quot; ii) Evaluation of voltage holding ratio &quot; in Example 1, and as a result, the voltage holding ratio was 99.2%.

Iii) Evaluation of heat resistance

To the vertically aligned liquid crystal display device manufactured as described above, a voltage of 5 V was first applied at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. The value at this time is defined as the initial voltage maintenance ratio (VHR _BF ).

The liquid crystal display element after the VHR _BF measurement was placed in an oven at 100 캜, and thermal stress was applied for 1,000 hours. Subsequently, the liquid crystal display element was allowed to stand at room temperature, cooled to room temperature, and 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 thermal stress was applied was determined by the following equation (2). The heat resistance of the vertical liquid crystal cell was evaluated as &quot; good &quot; when the rate of change was less than 5% and the heat resistance was evaluated as &quot; poor &quot;

VHR (%) = ((VHR _BF - VHR _AF ) / VHR _BF ) 100 (2)

Claims (12)

A liquid crystal aligning agent characterized by containing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride containing a compound represented by the following formula (1) with a diamine:

(In the formula (1), Y ¹ and Y ² each independently represent a divalent organic group,
Z ¹ and Z ² each independently represent a trivalent organic group,
Q is a 4-valent organic group, and
and n1 and n2 are each independently 0 or 1). The method according to claim 1,
Wherein n1 and n2 in the formula (1) are each 0. 3. The method of claim 2,
The unit represented by the following formula (T) in the formula (1) is a tetravalent group derived from a tetracarboxylic dianhydride, and
A unit consisting of Y ¹ -Z ¹ and a unit composed of Y ² -Z ² are each independently a liquid crystal aligning agent which is a trivalent group derived from a monoamino dicarboxylic acid compound:

(In the formula (T), Q is the same as that in the formula (1), and "*" represents a bonding hand). The method of claim 3,
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 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: 3,5: 6-2 anhydride, Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraon, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic acid At least one selected from the group consisting of acetic anhydride,
Wherein the monoaminodicarboxylic acid compound is at least one selected from the group consisting of asparaginic acid, glutamic acid, 2-aminoadipic acid, carbocysteine, 2,3-dicarboxy aniline, 3,4-dicarboxy aniline, Amino-1,2-dicarboxylic naphthalene, 7-amino-1,2-dicarboxylic naphthalene, 8-dicarboxylic naphthalene, Amino-1,2-dicarboxy naphthalene,
Amino-2,3-dicarboxy naphthalene, 6-amino-2,3-dicarboxy naphthalene, 7-amino- Amino-2,3-dicarboxy naphthalene, and 8-amino-2,3-dicarboxy naphthalene. The method of claim 3,
Wherein the compound represented by the formula (1) is obtained by reacting a tetracarboxylic acid dianhydride represented by the following formula (T-1) with a monoaminodicarboxylic acid compound followed by dehydration ring closure;

(In the formula (T-1), Q is the same as that in the formula (1)). 6. The method of claim 5,
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexa (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2 (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) - 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-2 anhydride, 4,9- Tricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic acid 2-anhydride, and at least one selected from the group consisting of
Wherein the monoaminodicarboxylic acid compound is at least one selected from the group consisting of asparaginic acid, glutamic acid, 2-aminoadipic acid, carbocysteine, 2,3-dicarboxy aniline, 3,4-dicarboxy aniline, Amino-1,2-dicarboxylic naphthalene, 7-amino-1,2-dicarboxylic naphthalene, 8-dicarboxylic naphthalene, Amino-1,2-dicarboxy naphthalene,
Amino-2,3-dicarboxy naphthalene, 6-amino-2,3-dicarboxy naphthalene, 7-amino- Amino-2,3-dicarboxy naphthalene, and 8-amino-2,3-dicarboxy naphthalene. The method according to claim 1,
Wherein n1 and n2 in the above formula (1) are each 1. 8. The method of claim 7,
The unit represented by the following formula (T) in the above formula (1) is a tetravalent group derived from a tetracarboxylic acid dianhydride,
Y ¹ and Y ² are, each independently, a divalent group derived from an aminoalcohol compound, and
Z ¹ and Z ² each independently represent a trivalent group derived from a halide of a tricarboxylic acid monoanhydride;

(In the formula (T), Q is the same as that in the formula (1), and "*" represents a bonding hand). 9. The method of claim 8,
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexa (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2 (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) - 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-2 anhydride, 4,9- Tricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic acid 2-anhydride, and at least one selected from the group consisting of
Wherein the amino alcohol compound is selected from the group consisting of aminomethanol, 2-aminoethanol, 1-amino-2-propanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 2-hydroxyaniline, And 4-hydroxyaniline, and at least one member selected from the group consisting of
The halide of the tricarboxylic acid monohydrate is a halide of 4-haloformylphthalic anhydride, propane-1,2,3-tricarboxylic acid monohydride, a halogen of butane-1,2,3-tricarboxylic acid monohydride Cargo, a halide of butane-1,2,4-tricarboxylic acid monoanhydride, a halide of pentane-1,2,3-tricarboxylic acid monoanhydride, a pentane-1,2,4-tricarboxylic acid monoanhydride A halide of pentane-1,2,5-tricarboxylic acid monohydrate, and a halide of cyclohexane-1,2,4-tricarboxylic acid monohydrate. 9. The method of claim 8,
Wherein the compound represented by the formula (1) is obtained by reacting a tetracarboxylic acid dianhydride represented by the following formula (T-1) with an aminoalcohol compound, and further reacting the compound with a halide of a tricarboxylic acid monohydrate. Aligner:

(In the formula (T-1), Q is the same as that in the formula (1)). 11. The method of claim 10,
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexa (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2 (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) - 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-2 anhydride, 4,9- Tricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic acid 2-anhydride, and at least one selected from the group consisting of
Wherein the amino alcohol compound is selected from the group consisting of aminomethanol, 2-aminoethanol, 1-amino-2-propanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 2-hydroxyaniline, And 4-hydroxyaniline, and at least one member selected from the group consisting of
The halide of the tricarboxylic acid monohydrate is a halide of 4-haloformylphthalic anhydride, propane-1,2,3-tricarboxylic acid monohydride, a halogen of butane-1,2,3-tricarboxylic acid monohydride Cargo, a halide of butane-1,2,4-tricarboxylic acid monoanhydride, a halide of pentane-1,2,3-tricarboxylic acid monoanhydride, a pentane-1,2,4-tricarboxylic acid monoanhydride A halide of pentane-1,2,5-tricarboxylic acid monohydrate, and a halide of cyclohexane-1,2,4-tricarboxylic acid monohydrate. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to any one of claims 1 to 11.