JP5120580B1 - Liquid crystal alignment agent - Google Patents

Abstract

（式（１）中、Ｙ^１およびＹ^２は、それぞれ独立に、２価の有機基であり、Ｚ^１およびＺ^２は、それぞれ独立に、３価の有機基であり、Ｑは４価の有機基であり、そしてｎ１およびｎ２は、それぞれ独立に、０または１である。）
【選択図】なしDisclosed is a liquid crystal aligning agent having characteristics superior to 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 comprising a polyamic acid obtained by reacting a tetracarboxylic dianhydride containing a compound represented by the following formula (1) with a diamine.

(In Formula (1), Y ¹ and Y ² are each independently a divalent organic group, Z ¹ and Z ² are each independently a trivalent organic group, and Q is a tetravalent organic group. And is an organic group, and n1 and n2 are each independently 0 or 1.)
[Selection figure] None

Description

The present invention relates to a liquid crystal aligning agent.
The present invention provides a liquid crystal aligning agent having characteristics superior to those of a liquid crystal aligning agent 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 requiring a polymer imidation step and a subsequent solvent replacement step.

The liquid crystal display element includes a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. This liquid crystal alignment film is generally formed through a step of applying a liquid crystal alignment agent containing a polymer on a substrate. As the polymer contained in the liquid crystal aligning agent, polyamic acid, imidized polymer of polyamic acid, polyamide, polyester, polyorganosiloxane, etc. are known, and in particular, partially imidized polymer of polyamic acid is soluble. And electric characteristics are compatible with each other (Patent Document 1).
A liquid crystal aligning agent containing a partially imidized polymer of polyamic acid is usually prepared through the following multi-step process. First, a step of reacting tetracarboxylic dianhydride and diamine in an organic solvent to synthesize a polyamic acid is performed. Next, a polyamic acid is partially imidized by adding a dehydrating agent and a dehydrating catalyst to the solution containing the polyamic acid and heating to obtain a partially imidized polymer. This imidization step requires a long time of about 4 to 6 hours, for example. In addition, since the dehydrating agent and the dehydration catalyst remain together with the target polymer in the reaction mixture obtained in this imidization step, a solvent replacement step or reprecipitation purification of the polymer is then performed to remove these. There is a need to do. Furthermore, a desired liquid crystal aligning agent will be finally obtained by mix | blending another component as needed.
Thus, in general, it takes a long time to prepare a liquid crystal aligning agent containing a partially imidized polymer of polyamic acid, and solvent replacement or reprecipitation is scheduled during the process. It is necessary to keep the reaction kettle to be a fraction of the original capacity of the reaction kettle, which further increases the manufacturing cost. Even the process of replacing the solvent of the solution containing the polymer alone has a significant energy cost.

JP-A-9-157392 JP 2010-97188 A

  The present invention has been made in order to overcome the above-described situation, and a liquid crystal alignment containing a partially imidized polymer of polyamic acid while omitting the imidization step of the polymer and the subsequent solvent replacement step. It aims at providing the liquid crystal aligning agent which has the characteristic which surpasses an agent.

According to the present invention, the above objects and advantages of the present invention are:
It is achieved by a liquid crystal aligning agent characterized by containing a polyamic acid obtained by reacting a tetracarboxylic dianhydride containing a compound represented by the following formula (1) with a diamine.

(In formula (1), Y ¹ and Y ² are each independently a divalent organic group,
Z ¹ and Z ² are each independently a trivalent organic group,
Q is a tetravalent organic group, 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 superior to those of a conventionally known liquid crystal aligning agent containing a partially imidized polymer of polyamic acid.
Since the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention has an imide ring derived from the raw material tetracarboxylic dianhydride, there is no need to go through an imidization step and a solvent substitution step after polymerization. . The cost for producing the tetracarboxylic dianhydride is very small compared to the costs for the imidization step and the solvent substitution step of the polymer, so the total cost for preparing the liquid crystal alignment agent Is reduced.
Furthermore, since the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention has a unique structure in which imide rings and amic acid units are alternately connected in the molecule, the liquid crystal aligning agent of the present invention containing this has It is possible to develop characteristics that could not be exhibited by conventional materials, for example, as uniform a film-forming ability as possible.

The liquid crystal aligning agent of this invention contains the polyamic acid obtained by making the tetracarboxylic dianhydride containing the compound represented by the said Formula (1) react with diamine.
It is preferable that n1 and n2 in the above formula (1) are both 0 or both.
When n1 and n2 in the above formula (1) are each 0, the compound represented by the above formula (1) is a tetracarboxylic dianhydride represented by the following formula (T-1) and a monoaminodicarboxylic acid. It can be obtained by reacting with an acid compound to obtain a tetracarboxylic acid compound as an intermediate compound, and then dehydrating and ring-closing the tetracarboxylic acid compound.

(In formula (T-1), Q has the same meaning as in formula (1) above.)
In this case, the unit represented by the following formula (T) in the above formula (1) is a tetravalent group derived from the tetracarboxylic dianhydride represented by the above formula (T-1).
The unit consisting of Y ¹ -Z ¹ and the unit consisting of Y ² -Z ² are trivalent groups derived from a monoaminodicarboxylic acid compound.

(In formula (T), Q has the same meaning as in formula (1) above, and “*” represents a bond, respectively.)
The tetravalent group derived from the tetracarboxylic dianhydride represented by the above formula (T-1) is obtained by removing two oxygen atoms constituting the ring from the tetracarboxylic dianhydride 4 A valent group;
The trivalent group derived from a monoaminodicarboxylic acid compound refers to a trivalent group obtained by removing an amino group and two carboxy groups from the monoaminodicarboxylic acid compound.

The tetracarboxylic dianhydride represented by the above formula (T-1) is a tetracarboxylic dianhydride known as one used for producing a polyamic acid contained in a liquid crystal aligning agent or an imidized polymer thereof. Anhydrides can be used without particular limitation. Examples of such tetracarboxylic dianhydrides include tetracarboxylic dianhydrides described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188). Particularly preferred tetracarboxylic dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5, 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 8-Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2 , 4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3, At least one selected from the group consisting of 5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride is there.

  Examples of the monoaminodicarboxylic acid compound include aspartic acid, glutamic acid, 2-aminoadipic acid, carbocysteine, 2,3-dicarboxyaniline, 3,4-dicarboxyaniline, and 3-amino-1,2-dicarboxyl. Naphthalene, 4-amino-1,2-dicarboxynaphthalene, 5-amino-1,2-dicarboxynaphthalene, 6-amino-1,2-dicarboxynaphthalene, 7-amino-1,2-dicarboxynaphthalene, 8-amino-1,2-dicarboxynaphthalene, 1-amino-2,3-dicarboxynaphthalene, 4-amino-2,3-dicarboxynaphthalene, 5-amino-2,3-dicarboxynaphthalene, 6- Amino-2,3-dicarboxynaphthalene, 7-amino-2,3-dicarboxynaphthalene, 8- Etc. can be mentioned amino-2,3-dicarboxynaphthalene, it is preferred to use at least one selected from among these.

The reaction of the tetracarboxylic dianhydride represented by the above formula (T-1) and the monoaminodicarboxylic acid compound can be carried out by heating these compounds, preferably in an appropriate solvent.
The ratio of both compounds in this reaction is preferably 1.0 to 4.0 moles as the use ratio of the monoaminodicarboxylic acid compound to 1 mole of tetracarboxylic dianhydride, More preferably, the molar ratio is 1.8 to 2.5 moles.
The solvent used in this reaction is preferably an organic solvent, and for example, an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc. are used. Can do.

Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea as the aprotic polar solvent. Hexamethylphosphotriamide, pyridine, 2-picoline, 3-picoline, 4-picoline and the like;
Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate;

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 ethyl ether acetate. Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran and the like;
Examples of the halogenated hydrocarbon include 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, isoamylpropionate, isoamylisobutyrate, diisopentyl ether, and the like, and one selected from these It is preferable to use the above.
The proportion of the solvent used is preferably 50 to 5,000 parts by weight, preferably 100 to 3,000 parts by weight, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the monoaminodicarboxylic acid compound. More preferably, it is more preferable to set it as 100-2,000 weight part.

  The reaction between the tetracarboxylic dianhydride and the monoaminodicarboxylic acid compound is preferably 50 to 300 ° C., more preferably 80 to 200 ° C., preferably 0.1 to 10 hours, more preferably 0.00. It is performed for 1 to 20 hours. If desired, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the above temperature and reaction time range.

By reacting the tetracarboxylic dianhydride and the monoaminodicarboxylic acid compound as described above, a tetracarboxylic acid compound as an intermediate compound is obtained. Subsequently, a dehydrating ring-closing reaction of this tetracarboxylic acid compound can yield a compound in which n1 and n2 are each 0 in the above formula (1).
The dehydration ring-closing reaction of the tetracarboxylic acid compound can be performed, 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 presence of a dehydration ring closure catalyst.
Examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.1 to 100 mol, and more preferably 2 to 100 mol, per 1 mol of the tetracarboxylic acid compound.

As the solvent used in the dehydration ring closure reaction, the solvents exemplified above as the solvent used in the reaction between the tetracarboxylic dianhydride represented by the above formula (T-1) and the monoaminodicarboxylic acid compound, It can be preferably used.
The use ratio of the solvent is preferably 500 parts by weight or less, and more preferably 100 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic acid compound and the dehydrating agent. In the most preferred embodiment of the present invention, no solvent is used for contacting the tetracarboxylic acid compound with the dehydrating agent.
Examples of the dehydration ring closure catalyst include tertiary amines such as pyridine, collidine, lutidine, and triethylamine. The use ratio of the dehydration ring closure catalyst is preferably 500 mol or less, more preferably 100 mol or less, per 1 mol of the dehydrating agent. In the most preferred embodiment of the present invention, no dehydration ring closure catalyst is used when the tetracarboxylic acid compound is contacted with the dehydrating agent.
The contact between the tetracarboxylic acid compound and the dehydrating agent is preferably performed at a temperature of 50 to 300 ° C., more preferably 80 to 200 ° C., preferably for 0.1 to 20 hours, more preferably for 0.1 to 10 hours. .
As described above, a compound in which n1 and n2 are each 0 in the above formula (1) can be obtained.

When n1 and n2 in the formula (1) are each 1, the compound represented by the formula (1) is a tetracarboxylic dianhydride and an amino alcohol compound represented by the formula (T-1). Can be obtained by further reacting the dihydroxy compound with a halide of tricarboxylic acid monoanhydride.
In this case, the unit represented by the above formula (T) in the above formula (1) is a tetravalent group derived from the tetracarboxylic dianhydride represented by the above formula (T-1).
Y ¹ and Y ² are divalent groups derived from an amino alcohol compound, and Z ¹ and Z ² are trivalent groups derived from a halide of tricarboxylic acid monoanhydride. The tetravalent group derived from the tetracarboxylic dianhydride represented by the above formula (T-1) is obtained by removing two oxygen atoms constituting the ring from the tetracarboxylic dianhydride 4 A valent group;
The divalent group derived from an amino alcohol compound refers to a divalent group obtained by removing an amino group and a hydroxyl group from the amino alcohol compound; and a trivalent group derived from a halide of tricarboxylic acid monoanhydride. The group is a halide of the tricarboxylic acid monoanhydride to an acid anhydride group (group —C (═O) —O—C (═O) —) and group —COOX (where X is a halogen atom). ) Is a trivalent group obtained by removing.
The tetracarboxylic dianhydride represented by the above formula (T-1) is the same as described above for the case where n1 and n2 in the above formula (1) are each 0.

Examples of the amino alcohol compound include aminomethanol, 2-aminoethanol, 1-amino-2-propanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 2-hydroxyaniline, and 3-hydroxy. Aniline, 4-hydroxyaniline, etc. can be mentioned, It is preferable to use at least 1 sort (s) selected from these.
Examples of the tricarboxylic acid monoanhydride halide include 4-haloformylphthalic anhydride, propane-1,2,3-tricarboxylic acid monoanhydride, butane-1,2,3-tricarboxylic acid monohydride. Anhydride halide, Butane-1,2,4-tricarboxylic acid monoanhydride halide, Pentane-1,2,3-tricarboxylic acid monoanhydride halide, Pentane-1,2,4-tricarboxylic acid Monoanhydride halide, pentane-1,2,5-tricarboxylic acid monoanhydride halide, cyclohexane-1,2,4-tricarboxylic acid monoanhydride halide, and the like. It is preferable to use at least one selected from Examples of the halogen atom contained in the tricarboxylic acid monoanhydride halide include a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom is preferred.

The reaction between the tetracarboxylic dianhydride represented by the above formula (T-1) and the amino alcohol compound can be performed by heating these compounds, preferably in an appropriate solvent.
The ratio of both compounds in this reaction is preferably 1 to 5 moles, more preferably 1 to 3 moles, as the use ratio of the amino alcohol compound to 1 mole of tetracarboxylic dianhydride.
As the solvent used in this reaction, the solvents exemplified above as the solvent used in the reaction between the tetracarboxylic dianhydride represented by the above formula (T-1) and the monoaminodicarboxylic acid compound are preferable. Can be used.
The use ratio of the solvent is preferably 50 to 5,000 parts by weight and preferably 100 to 3,000 parts by weight with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and the amino alcohol compound. More preferably, it is more preferable to set it as 100-2,000 weight part.
The reaction between the tetracarboxylic dianhydride and the aminoalcohol compound is preferably at a temperature of 50 to 300 ° C, more preferably 80 to 200 ° C, preferably 0.1 to 10 hours, more preferably 0.1. ~ 20 hours. If desired, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the above temperature and reaction time range.

By the reaction of tetracarboxylic dianhydride and amino alcohol compound as described above, a dihydroxy compound as an intermediate compound is obtained. Next, by reacting this dihydroxy compound with a halide of tricarboxylic acid monoanhydride, a compound in which n1 and n2 are each 1 in the above formula (1) can be obtained. This reaction can be carried out by heating these compounds, preferably in a suitable solvent.
The proportion of both compounds in this reaction is preferably 2 to 5 mol, and preferably 2 to 3 mol, as the proportion of tricarboxylic monoanhydride halide used per mol of the dihydroxy compound.
As the solvent used in this reaction, the solvents exemplified above as the solvent used in the reaction between the tetracarboxylic dianhydride represented by the above formula (T-1) and the monoaminodicarboxylic acid compound are preferable. Can be used.
The use ratio of the solvent is preferably 50 to 5,000 parts by weight, preferably 100 to 3,000 parts by weight, based on 100 parts by weight of the total of the dihydroxy compound and the tricarboxylic acid monoanhydride halide. Is more preferable.
The reaction between the dihydroxy compound and the halide of tricarboxylic acid monoanhydride is preferably -50 to 150 ° C, more preferably 0 to 100 ° C, and preferably 0.1 to 30 hours, more preferably 0.00. 1 to 15 hours. If desired, the reaction may be carried out while raising the reaction temperature stepwise or continuously.
As described above, 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 tetracarboxylic dianhydride containing the compound represented by the above formula (1) obtained as described above with a diamine. .
As the tetracarboxylic dianhydride used for synthesizing the polyamic acid, only the compound represented by the above formula (1) may be used, or together with the compound represented by the above formula (1). Other tetracarboxylic dianhydrides may be used in combination. Examples of other tetracarboxylic dianhydrides that can be used in combination here include tetracarboxylic dianhydrides represented by the above formula (T-1), and particularly preferably 1, 2, 3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran) -2 ', 5'- ON), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane- 2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3. 0] At least one selected from the group consisting of octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride.
The tetracarboxylic dianhydride used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of the present invention is a compound represented by the above formula (1) with respect to all the tetracarboxylic dianhydrides. The content is preferably 20 mol% or more, more preferably 50 mol% or more, and 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′-. Diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, dodecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5- Diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-di Minobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid Cholestenyl acid, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, etc. In addition, diamines described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188) can be used, and it is preferable to use one or more selected from these.

The ratio of the tetracarboxylic dianhydride and diamine used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0 with respect to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably carried out in an appropriate solvent, preferably at a temperature of -20 to 150 ° C, more preferably at a temperature of 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably 2 to 2. 10 hours. Examples of the solvent used here include N-methyl-2-pyrrolidone and γ-butyrolactone, and it is preferable to use one or more selected from these.
For the polyamic acid, the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. is there. The ratio (Mw / Mn) between this Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. When Mw and Mw / Mn of the polyamic acid are in the above ranges, the liquid crystal aligning agent containing the polyamic acid achieves both stability as a composition and good liquid crystal alignment of the formed liquid crystal alignment film. This is preferable.

The liquid crystal aligning agent of the present invention preferably contains the polyamic acid obtained as described above, but may contain other components in addition to this, as long as the effects of the present invention are not diminished. Examples of other components that can be used here include an epoxy compound and a functional silane compound. 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 composition in which the above polyamic acid and other optional components are dissolved in a suitable solvent. Examples of the solvent used for the liquid crystal aligning agent include N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, propylene glycol monomethyl ether, ethyl cellosolve, 2 , 3-pentanedione, 1,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane, etc. can be used, and one or more selected from these can be used. it can.
The solid content concentration of the liquid crystal aligning agent (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 preferably in the range of 1 to 10 wt%.

The liquid crystal display element of the present invention comprises two substrates on which a liquid crystal alignment film is formed as a pair, and the liquid crystal is arranged in a gap in which the pair of substrates are arranged close to each other so that the liquid crystal alignment film faces each other. Is done. Here, the pair of substrates has at least a pair of electrodes. This electrode pair is
It may consist of electrodes formed on the surfaces of each of the two substrates and generate an electric field in a direction perpendicular to the substrate surface; It may generate an electric field in the horizontal direction with respect to the surface.
The liquid crystal alignment film can be formed on the substrate by applying the liquid crystal aligning agent of the present invention on the substrate by a known method and then heating to form a coating film. You may give a well-known rubbing process to the formed coating film as needed.

Since the polyamic acid contained in the liquid crystal aligning agent of the present invention has a unique and uniform structure in which imide rings and amic acid units are alternately linked in the molecule, the liquid crystal aligning agent of the present invention containing this has the following properties: An extremely uniform coating film forming ability can be expressed. Therefore, the liquid crystal alignment film formed from the liquid crystal aligning agent of this invention is excellent in in-plane uniformity.
The liquid crystal display element of the present invention comprising a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is excellent in liquid crystal alignment uniformity, electrical characteristics, afterimage characteristics, and the like.

<Synthesis of tetracarboxylic dianhydride represented by formula (1)>
Synthesis Example A-1
Compound (A-1) was synthesized according to the following scheme 1.

A 2 L three-necked flask equipped with a reflux tube was charged with 218.12 g of pyromellitic dianhydride, 266.2 g of L-aspartic acid and 1,000 mL of pyridine, stirred at 45 ° C. for 2 hours, and then reacted under reflux for 4 hours. Went. After the reaction, the solvent was removed by distillation under reduced pressure to obtain 448 g of compound (A-1a).
Subsequently, 448 g of the compound (A-1a) obtained above and 700 g of acetic anhydride were charged and mixed in a 1 L three-necked flask equipped with a reflux tube, reacted for 4 hours under reflux, and then anhydrous by vacuum distillation. By removing acetic acid, 400 g of the target compound (A-1) was obtained.

Synthesis Example A-2
Compound (A-2) was synthesized according to the following scheme 2.

A 2 L three-necked flask equipped with a reflux tube was charged with 218.12 g of pyromellitic dianhydride, 362.3 g of 3,4-dicarboxyaniline and 1,000 mL of dimethylformamide, and stirred at 45 ° C. for 2 hours. The reaction was then carried out under reflux for 4 hours. After the reaction, the solvent was removed by distillation under reduced pressure to obtain 540 g of Compound (A-2a).
Subsequently, 540 g of the compound (A-2a) obtained above and 700 g of acetic anhydride were charged and mixed in a 1 L three-necked flask equipped with a reflux tube, reacted for 4 hours under reflux, and then anhydrous by vacuum distillation. By removing acetic acid, 495 g of the target compound (A-2) was obtained.

Synthesis Example A-3
Compound (A-2) was synthesized according to the following scheme 3.

A 2 L three-necked flask equipped with a reflux tube was charged with 224.17 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 122.16 g of 2-aminoethanol and 1,000 mL of dimethylformamide, and mixed at 45 ° C. The mixture was stirred for 4 hours and then reacted under reflux for 4 hours. After the reaction, the solvent was removed by distillation under reduced pressure to obtain 308 g of Compound (A-3a).
Subsequently, 308 g of the compound (A-3a) obtained above and 400 mL of tetrahydrofuran (THF) were charged and dissolved in a 2 L three-necked flask equipped with a dropping funnel, and 400 g of triethylamine was further added. Under ice cooling, a solution prepared by dissolving 421.14 g of 4-chloroformylphthalic anhydride in 800 mL of tetrahydrofuran was slowly added dropwise from a dropping funnel. After completion of the dropping, the reaction was carried out by stirring at room temperature for 3 hours. After the reaction, triethylamine hydrochloride formed as a by-product from the reaction mixture was filtered off, THF was removed by distillation under reduced pressure, and 1,000 mL of chloroform was added to make a solution. The obtained 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 Compound (A-3).

<Synthesis of polyamic acid>
Synthesis Example P-1
16.639 g of the compound (A-1) obtained in Synthesis Example A-1 as tetracarboxylic dianhydride, 7.842 g of 4,4′-diaminodiphenylmethane and 3,6-bis (4-aminobenzoyloxy) as diamine ) 0.519 g of cholestane was dissolved in 100 g of N-methyl-2-pyrrolidone and reacted 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 under reduced pressure at 40 ° C. for 15 hours to obtain 24.2 g of polyamic acid (P-1).

Synthesis Example P-2
17.762 g of the compound (A-2) obtained in Synthesis Example A-2 as tetracarboxylic dianhydride, 6.789 g of 4,4′-diaminodiphenylmethane as diamine and 3,6-bis (4-aminobenzoyloxy) ) 0.449 g of cholestane was dissolved in 100 g of N-methyl-2-pyrrolidone and reacted 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 ° C. under reduced pressure for 15 hours to obtain 24.6 g of polyamic acid (P-2).

Synthesis Example P-3
19.018 g of compound (A-3) obtained in Synthesis Example A-3 as tetracarboxylic dianhydride and 5.611 g of 4,4′-diaminodiphenylmethane and 3,6-bis (4-aminobenzoyloxy) as diamine ) 0.371 g of cholestane was dissolved in 100 g of N-methyl-2-pyrrolidone and reacted 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 ° C. under reduced pressure for 15 hours 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 dianhydride and 3.597 g of p-phenylenediamine and 4.348 g of 3 (3,5-diaminobenzoyloxy) cholestane as diamine Was dissolved in 100 g of N-methyl-2-pyrrolidone and reacted 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 under reduced pressure at 40 ° C. for 15 hours to obtain 24.5 g of polyamic acid (P-4).

Comparative Synthesis Example rp-1
12.822 g of pyromellitic dianhydride as tetracarboxylic dianhydride and 11.422 g of 4,4′-diaminodiphenylmethane and 0.756 g of 3,6-bis (4-aminobenzoyloxy) cholestane as N-methyl as diamine The product was dissolved in 100 g of 2-pyrrolidone and reacted 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 under reduced pressure at 40 ° C. for 15 hours to obtain 24.1 g of polyamic acid (rp-1).

Comparative Synthesis Example rp-2
12.822 g of pyromellitic dianhydride as tetracarboxylic dianhydride and 11.422 g of 4,4′-diaminodiphenylmethane and 0.756 g of 3,6-bis (4-aminobenzoyloxy) cholestane as N-methyl as diamine The product was dissolved in 100 g of 2-pyrrolidone and reacted at room temperature for 6 hours. Next, 125 g of NMP was added to the obtained polyamic acid solution, 4.65 g of pyridine and 6 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 80 ° C. for 3 hours. Thereafter, the obtained 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 ° C. under reduced pressure for 15 hours to obtain 23.8 g of polyimide (rp-2) having an imidization ratio of 50%.

<Preparation and evaluation of liquid crystal aligning agent>
Example 1
(1) Preparation of liquid crystal aligning agent The polyamic acid (P-1) obtained in Synthesis Example P-1 was mixed with N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (NMP: BC = 50). : 50 (mass ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering through a filter having a pore size of 0.2 μm.
(2) Evaluation of printability About the liquid crystal aligning agent prepared above, it apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printer (Nissha Printing Co., Ltd.), After removing the solvent by heating (pre-baking) for 1 minute on an 80 ° C. hot plate, heating (post-baking) for 10 minutes on a 200 ° C. hot plate to form a coating film having an average film thickness of 600 mm. When this coating film was observed with a microscope with a magnification of 20 times to check for the presence of printing unevenness and pinholes, neither printing unevenness nor pinholes were observed, and the printability was good.
(3) Evaluation of film thickness uniformity of coating film Using the stylus film thickness meter (manufactured by KLA Tencor) for the coating film formed above, the film thickness at the center of the substrate and the center of 15 mm from the outer edge of the substrate The film thickness at the position near the film was measured. When the film thickness difference between the two positions was 20 mm or less, the film thickness uniformity was “good”, and when the film thickness difference was more than 20 mm, the film thickness uniformity was “bad”. The property was good.

(4) Manufacture of TN type liquid crystal cell The liquid crystal aligning agent prepared above is 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 printer (Nissha Printing Co., Ltd.). Then, after removing the solvent by heating (pre-baking) on an 80 ° C. hot plate for 1 minute, heating (post-baking) on a 200 ° C. hot plate for 10 minutes to form a coating film having an average film thickness of 600 mm . The coating film is rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm to give liquid crystal alignment ability. did. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film.
The above operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, the liquid crystal alignment film surfaces of the pair of substrates are relative to each other. The adhesive was cured by overlapping and pressing. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, whereby a TN type liquid crystal cell. Manufactured.

(5) Evaluation of liquid crystal cell i) Evaluation of liquid crystal alignment The liquid crystal cell produced above was observed with a microscope for the presence or absence of abnormal domains when the voltage was turned on / off under crossed Nicols, and abnormal domains were observed. When it was not evaluated, the liquid crystal orientation was “good”, and when the abnormal domain was observed, the liquid crystal orientation was evaluated as “bad”. The liquid crystal orientation of this liquid crystal cell was “good”.
ii) Evaluation of voltage holding ratio After the voltage of 5 V was applied to the liquid crystal display device manufactured as described above for a duration of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio after 167 milliseconds from release of application was measured. did. As a measuring apparatus, VHR-1 manufactured by Toyo Corporation was used.
As a result, the voltage holding ratio of this liquid crystal display element was 98.8%.
iii) Evaluation of afterimage characteristics For the liquid crystal display device manufactured above, a voltage of 17 V DC was applied for 20 hours at an environmental temperature of 100 ° C., and the voltage remaining in the liquid crystal cell immediately after the DC voltage was turned off (residual DC voltage) Was obtained by flicker elimination while irradiating with backlight. The value of the residual DC voltage of this liquid crystal display element was 20 mV.
It has been empirically revealed that the afterimage characteristics are good when the value of the residual DC voltage obtained by the flicker erasing method while irradiating this backlight light is 100 mV or less.

Examples 2 and 3 and Comparative Examples 1 and 2
In Example 1, instead of the polyamic acid (P-1), the polyamic acids P-2 and P-3 obtained in the above synthesis examples and the polyamic acids rp-1 and rp-2 obtained in the comparative synthesis examples were used, respectively. The liquid crystal aligning agent was prepared 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 mixed with N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (NMP: BC = 50). : 50 (mass ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering through a filter having a pore size of 0.2 μm.
(2) Evaluation of printability Using the liquid crystal aligning agent prepared above, a coating film was formed in the same manner as in “(2) Evaluation of printability” in Example 1, and the printability of the liquid crystal aligning agent was examined. As a result, neither printing unevenness nor pinholes were observed by observation with a microscope with a magnification of 20 times, and the printability was good.
(3) Evaluation of film thickness uniformity of coating film For the coating film formed as described above, the film thickness is uniform by the same method and criteria as in "(3) Evaluation of film thickness uniformity of coating film" in Example 1 above. The film thickness uniformity of this coating film was good.

(4) Manufacture of vertical liquid crystal cell The liquid crystal aligning agent prepared above is applied to a liquid crystal alignment film printer (Nissha Printing Co., Ltd.) on the transparent electrode surface of a glass substrate with a transparent electrode (thickness 1 mm) made of ITO film. )), And heated (pre-baked) for 1 minute on a hot plate at 80 ° C. and further heated (post-baked) for 60 minutes on a hot plate at 200 ° C. Liquid crystal alignment film) was formed. This operation was repeated to obtain a pair (two) of glass substrates having a liquid crystal alignment film on the transparent conductive film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, the liquid crystal alignment film surfaces of the pair of substrates are relative to each other. The adhesive was cured by overlapping and pressing. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, whereby a vertical liquid crystal cell is obtained. Manufactured.

(5) Evaluation of liquid crystal cell i) Evaluation of liquid crystal alignment The liquid crystal cell manufactured above was evaluated for liquid crystal alignment in the same manner as in “i) Evaluation of liquid crystal alignment” in Example 1. No abnormal domain was observed, and the liquid crystal alignment was “good”.
ii) Evaluation of voltage holding ratio The voltage holding ratio of the liquid crystal cell produced above was measured in the same manner as in “ii) Evaluation of voltage holding ratio” in Example 1, and the voltage holding ratio was 99.2%. It was.
iii) Evaluation of heat resistance With respect to the vertical alignment type liquid crystal display device manufactured as described above, first, a voltage of 5 V is applied with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage is maintained 167 milliseconds after the application is released. The rate was measured. The numerical value at this time was defined as the initial voltage holding ratio (VHR _BF ).
The liquid crystal display element after the VHR _BF measurement was put in an oven at 100 ° C., and thermal stress was applied for 1,000 hours. Next, the liquid crystal display element was allowed to stand at room temperature and cooled to room temperature, and then the voltage holding ratio (VHR _AF ) after application of thermal stress was measured under the same conditions as the measurement of the initial voltage holding ratio.
Then, the change rate (ΔVHR) of the voltage holding ratio before and after application of the thermal stress was obtained by the following mathematical formula (2). When the rate of change was less than 5%, the heat resistance was evaluated as “good”. When the rate of change was 5% or more was evaluated as “heat resistance”, the heat resistance of the vertical liquid crystal cell was “good”. It was.
_{△ VHR (%) = ((} VHR BF -VHR AF) ÷ VHR BF) × 100 (2)

Claims (12)

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

(In formula (1), Y ¹ and Y ² are each independently a divalent organic group,
Z ¹ and Z ² are each independently a trivalent organic group,
Q is a tetravalent organic group, and n1 and n2 are each independently 0 or 1. )   The liquid crystal aligning agent of Claim 1 whose n1 and n2 in said Formula (1) are 0, respectively. The unit represented by the following formula (T) in the above formula (1) is a tetravalent group derived from tetracarboxylic dianhydride, and from the unit consisting of Y ¹ -Z ¹ and Y ² -Z ² The liquid crystal aligning agent according to claim 2, wherein the units are each independently a trivalent group derived from a monoaminodicarboxylic acid compound.

(In formula (T), Q has the same meaning as in formula (1) above, and “*” represents a bond, respectively.) The tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b. -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, 3,5 6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8, One or more selected from the group consisting of 10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride, and Monoaminodicarboxylic acid compounds are aspartic acid, glutamic acid, 2-aminoadipic acid, carbocysteine, 2,3-dicarboxyaniline, 3,4-dicarboxyaniline, 3-amino-1,2-dicarboxynaphthalene, 4 -Amino-1,2-dicarboxynaphthalene, 5-amino-1,2-dicarboxynaphthalene, 6-amino-1,2-dicarboxynaphthalene, 7-amino -1,2-dicarboxynaphthalene, 8-amino-1,2-dicarboxynaphthalene,
1-amino-2,3-dicarboxynaphthalene, 4-amino-2,3-dicarboxynaphthalene, 5-amino-2,3-dicarboxynaphthalene, 6-amino-2,3-dicarboxynaphthalene, 7- The liquid crystal aligning agent of Claim 3 which is at least 1 sort (s) selected from the group which consists of amino-2,3-dicarboxynaphthalene and 8-amino-2,3-dicarboxynaphthalene. A compound obtained by reacting a tetracarboxylic dianhydride represented by the following formula (T-1) with a monoaminodicarboxylic acid compound and then dehydrating and ring-closing the compound represented by the above formula (1) The liquid crystal aligning agent of Claim 3 which is.

(In formula (T-1), Q has the same meaning as in formula (1) above.) The tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b- Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4 -Dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, 3,5,5 - tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10 -One or more selected from the group consisting of tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride, and the above mono The aminodicarboxylic acid compound is aspartic acid, glutamic acid, 2-aminoadipic acid, carbocysteine, 2,3-dicarboxyaniline, 3,4-dicarboxyaniline, 3-amino-1,2-dicarboxynaphthalene, 4- Amino-1,2-dicarboxynaphthalene, 5-amino-1,2-dicarboxynaphthalene, 6-amino-1,2-dicarboxynaphthalene, 7-amino- 1,2-dicarboxynaphthalene, 8-amino-1,2-dicarboxynaphthalene,
1-amino-2,3-dicarboxynaphthalene, 4-amino-2,3-dicarboxynaphthalene, 5-amino-2,3-dicarboxynaphthalene, 6-amino-2,3-dicarboxynaphthalene, 7- The liquid crystal aligning agent of Claim 5 which is at least 1 sort (s) selected from the group which consists of amino-2,3-dicarboxynaphthalene and 8-amino-2,3-dicarboxynaphthalene.   The liquid crystal aligning agent of Claim 1 whose n1 and n2 in the said Formula (1) are 1, respectively. The unit represented by the following formula (T) in the above formula (1) is a tetravalent group derived from tetracarboxylic dianhydride,
Y ¹ and Y ² are each independently a divalent group derived from an amino alcohol compound, and Z ¹ and Z ² are each independently a trivalent group derived from a halide of tricarboxylic acid monoanhydride. The liquid crystal aligning agent of Claim 7 which is group.

(In formula (T), Q has the same meaning as in formula (1) above, and “*” represents a bond, respectively.)
The tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b- Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4 -Dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, 3,5,5 - tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10 -One or more selected from the group consisting of tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride,
The amino alcohol compound is aminomethanol, 2-aminoethanol, 1-amino-2-propanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 2-hydroxyaniline, 3-hydroxyaniline and 4 -At least one selected from the group consisting of hydroxyaniline, and the halide of the tricarboxylic acid monoanhydride is 4-haloformylphthalic anhydride, propane-1,2,3-tricarboxylic acid monoanhydride Halide, Halide of propane-1,2,3-tricarboxylic acid monoanhydride, Halide of butane-1,2,3-tricarboxylic acid monoanhydride, Butane-1,2,4-tricarboxylic acid monoanhydride Halides of pentane-1,2,3-tricarboxylic acid monoanhydride Halides of pentane-1,2,4-tricarboxylic acid monoanhydride, halides of pentane-1,2,5-tricarboxylic acid monoanhydride and cyclohexane-1,2,4-tricarboxylic acid monoanhydride The liquid crystal aligning agent of Claim 8 which is at least 1 sort (s) selected from the group which consists of the halide of a thing. After the compound represented by the above formula (1) is reacted with a tetracarboxylic dianhydride represented by the following formula (T-1) and an amino alcohol compound, a tricarboxylic acid monoanhydride halide and The liquid crystal aligning agent of Claim 8 which is obtained by making it react.

(In formula (T-1), Q has the same meaning as in formula (1) above.) The tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b- Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4 -Dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, 3,5,5 - tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10 -One or more selected from the group consisting of tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride,
The amino alcohol compound is aminomethanol, 2-aminoethanol, 1-amino-2-propanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 2-hydroxyaniline, 3-hydroxyaniline and 4 -At least one selected from the group consisting of hydroxyaniline, and the halide of the tricarboxylic acid monoanhydride is 4-haloformylphthalic anhydride, propane-1,2,3-tricarboxylic acid monoanhydride Halide, Halide of propane-1,2,3-tricarboxylic acid monoanhydride, Halide of butane-1,2,3-tricarboxylic acid monoanhydride, Butane-1,2,4-tricarboxylic acid monoanhydride Halides of pentane-1,2,3-tricarboxylic acid monoanhydride Halides of pentane-1,2,4-tricarboxylic acid monoanhydride, halides of pentane-1,2,5-tricarboxylic acid monoanhydride and cyclohexane-1,2,4-tricarboxylic acid monoanhydride The liquid crystal aligning agent of Claim 10 which is at least 1 sort (s) selected from the group which consists of a halide of a thing.   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.