JP5668922B2 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element.
More specifically, a liquid crystal aligning agent and a display quality that can provide a liquid crystal display element that does not easily deteriorate in display quality when continuously driven for a long time, and exhibit good reworkability in the manufacturing process of the liquid crystal alignment film. The present invention relates to a liquid crystal display element that is excellent in display quality and does not deteriorate in display quality even when continuously driven for a long time.

Currently, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type, IPS (In-Plane Switching) type, OCB (Optical Compensated Bend) optical type such as compensation type Bend: Various liquid crystal display elements are known.
As materials for the liquid crystal alignment film having a function of aligning liquid crystal molecules in these liquid crystal display elements, resin materials such as polyamic acid, polyimide, polyamide, and polyester are known, and in particular, a liquid crystal alignment film made of polyamic acid or polyimide. Is excellent in heat resistance, mechanical strength, affinity with liquid crystal, etc., and is used in many liquid crystal display elements (Patent Documents 1 to 6).
In recent years, studies on improvement of display quality such as high definition of liquid crystal display elements and reduction of power consumption have progressed, and the range of use of liquid crystal display elements has been expanded. In particular, the use of liquid crystal televisions, which are expected to be used under conditions where the usage environment such as brightness and driving time is more severe than that of conventional liquid crystal display elements, is expanding with the momentum to expel conventional CRT televisions. Accordingly, there is a demand for a liquid crystal display element that has a higher display quality and does not deteriorate the display quality even when continuous driving is performed for a long time. However, a liquid crystal display element having a liquid crystal alignment film made of a polyamic acid or polyimide known in the past, when subjected to continuous driving for a long time, deteriorates the liquid crystal alignment film due to heat or light, and the electric characteristics of the liquid crystal cell. It has been pointed out that the display quality may deteriorate significantly due to deterioration. For this reason, there is a need for the development of a liquid crystal alignment film that does not cause deterioration that degrades display quality such as deterioration of electrical characteristics even when driven continuously for a long time (excellent long-term reliability). Yes.

By the way, a defective substrate (a substrate on which a film including defects such as pinholes in coating and uneven coating) formed in the liquid crystal alignment film forming process in liquid crystal panel production is peeled off from the defective coating on the substrate. In many cases, the substrate is reused. Therefore, from such a viewpoint, a liquid crystal alignment film material having good peelability is desired.
Now, for the purpose of realizing the above-described liquid crystal alignment film material having excellent long-term reliability, liquid crystal alignment agents containing polyfunctional epoxy compounds together with polyamic acid or polyimide have been proposed (Patent Documents 7 and 8). However, the liquid crystal aligning agent containing many polyfunctional epoxies to such an extent that long-term reliability is improved includes a problem that the peelability of the coating film once formed is remarkably inferior. It will be inferior to (reworkability).
Therefore, development of a liquid crystal alignment film material having both long-term reliability and reworkability is eagerly desired.

JP-A-4-153622 JP 60-107020 A JP 56-91277 A U.S. Pat. No. 5,928,733 Japanese Patent Laid-Open No. 62-165628 Japanese Patent Laid-Open No. 11-258605 Japanese Patent No. 3799700 JP 2008-299318 A JP-A-6-222366 JP-A-6-281937 JP-A-5-107544 JP 2010-97188 A

The present invention has been made in view of the above circumstances, and its purpose is:
A liquid crystal alignment film material that does not cause deterioration such as deterioration of display characteristics such as deterioration of electrical characteristics even when driven continuously for a long time, and is excellent in peelability of a coating film once formed. It is to provide.
Another object of the present invention is to provide a liquid crystal display element that is excellent in display quality and does not deteriorate in display quality even when continuously driven for a long time.
Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above-mentioned objects and advantages of the present invention are as follows.
(A) At least one polymer selected from the group consisting of polyamic acid and polyimide (hereinafter referred to as “polymer (A)”), and (B) the following formula (B)

(In the formula (B), ^{R I} is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
E is a group having a 1,2-epoxy structure;
X is a single bond, ^* —COO—, ^* —CO—, ^* —COO—CH ₂ — (the bond with “*” in the above is bonded to a nitrogen atom), a methylene group or 2 to 5 carbon atoms. An alkylene group of
Aro is a phenyl group, a naphthalene group or a biphenylyl group, and these groups are an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms. May be substituted )
(Hereinafter referred to as “compound (B)”)
It is achieved by a liquid crystal aligning agent containing
The above objects and advantages of the present invention are, secondly,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention can provide a liquid crystal aligning film that does not cause deterioration that causes deterioration in display quality, such as deterioration in electrical characteristics, even when continuously driven for a long time. Excellent peelability of the coated film.
The liquid crystal display element of the present invention having a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is excellent in display quality and does not deteriorate in display quality even when driven continuously for a long time. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, portable information terminals, digital cameras, cellular phones, various types. Used in display devices such as monitors and liquid crystal televisions.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention is as described above.
(A) At least one polymer selected from the group consisting of polyamic acid and polyimide (hereinafter referred to as “polymer (A)”) and (B) a compound represented by the above formula (B) (hereinafter referred to as “polymer”). (Referred to as “compound (B)”)
Containing.

<Polymer (A)>
The polymer (A) in the present invention is at least one polymer selected from the group consisting of polyamic acid and polyimide.
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride and diamine, and the polyimide can be obtained by dehydrating and ring-closing the polyamic acid.

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, and the like. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 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- No 1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2 : 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like;
As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride can be mentioned, respectively,
The tetracarboxylic dianhydride described in Patent Document 12 (Japanese Patent Laid-Open No. 2010-97188) can be used.

Among these, the tetracarboxylic dianhydride used for synthesizing the polyamic acid preferably includes an alicyclic tetracarboxylic dianhydride, and 2,3,5-tricarboxycyclopentyl. It is preferable that it contains at least one selected from the group consisting of acetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
The tetracarboxylic dianhydride used to synthesize the polyamic acid comprises 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. It is preferable that at least one selected from the group contains 10 mol% or more, more preferably 20 mol% or more, more preferably 2,3,5-tricarboxyl, based on the total tetracarboxylic dianhydride. Most preferably, it is composed of at least one selected from the group consisting of cyclopentylacetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[Diamine]
Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane and the like. Specific examples thereof include aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;
Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N , N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, Lestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3 , 6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4 -((Aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1 -Bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane and the following formula (A-1)

(In the formula (A-1), ^{X I} is an alkyl group having 1 to 3 carbon ^atoms, * ^-O-, * -COO- or ^* -OCO- (where bond marked with "*" is diaminophenyl group And a is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20.)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, respectively.
Diamines described in Patent Document 12 (Japanese Patent Application Laid-Open No. 2010-97188) can be used.
The ^{X I} in the above formula (A-1) an alkyl group having 1 to 3 carbon ^atoms, * -O- or ^* -COO- (provided that a bond marked with "*" is bonded to the diamino phenyl group.) In Preferably there is. Specific examples of the group C _c H _{2c + 1} — include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n -An eicosyl group etc. can be mentioned. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.
Specific examples of the compound represented by the formula (A-1) include, for example, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2, 4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, Octadecanoxy-2,5-diaminobenzene, the following formulas (A-1-1) to (A-1-3)

And the like, and the like.
In the above formula (A-1), it is preferable that a and b are not 0 at the same time.
The diamine used when synthesizing the polyamic acid in the present invention preferably contains the aromatic diamine as described above in an amount of 30 mol% or more, more preferably 50 mol% or more, based on the total diamine. In particular, it is preferable to contain 80 mol% or more.

When the liquid crystal aligning agent of the present invention is applied to a VA type liquid crystal display element, the diamine used when synthesizing the polyamic acid shall contain an aromatic diamine at a certain ratio as described above,
From the viewpoint of imparting appropriate pretilt angle expression, at least a part of the aromatic diamine is converted to cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2, 4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6- Bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5- Diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) Enyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4 Selected from the group consisting of -heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane and the compound represented by the above formula (A-1). It is preferable to use at least one kind of diamine (pretilt angle-expressing diamine), more preferably 5 mol% or more of these pretilt angle-expressing diamines, and more preferably 10 mol% or more. More preferably, the However, from the viewpoint of ensuring good coatability of the obtained liquid crystal aligning agent, the proportion of these pretilt angle-expressing diamines is preferably 90 mol% or less, and more preferably 70 mol% or less. preferable.

[Molecular weight regulator]
When synthesizing the polyamic acid, a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and dimian as described above. By making the specific polymer into such a terminal-modified polymer, the coating property (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.
Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples thereof include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic. Acid anhydride, n-hexadecyl succinic acid anhydride, etc .;
Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine;
Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

[Synthesis of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent.
The polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0-100 ° C, preferably 0.1-24 hours, more preferably 0.5-12 hours. Done.

Here, examples of the organic solvent include an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, and hydrocarbon. 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, etc .;
Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methanol, ethanol, isopropanol, 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, isoamyl propionate, isoamyl isobutyrate, diethyl oxalate, and malonic acid. Diethyl etc .;
Examples of the ether include diethyl ether, diisopentyl 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, etc .;
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, and the like.

Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and derivatives thereof (first group organic solvent), or one selected from the first group of organic solvents It is preferable to use a mixture of the above and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (second group organic solvent). In the latter case, the use ratio of the second group of organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, with respect to the total of the first group of organic solvents and the second group of organic solvents. Furthermore, it is preferable that it is 30 weight% or less.
The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. It is preferable.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained.
This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to a known method.

[Synthesis of polyimide]
The polyimide can be obtained by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize.
The polyimide in the present invention may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure that the polyamic acid that is a precursor thereof has, or by dehydrating and cyclizing only a part of the amic acid structure, A partially imidized product in which a structure and an imide ring structure coexist may be used. The polyimide in the present invention preferably has an imidization ratio of 30% or more, and more preferably 40% or more. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.
The polyamic acid is preferably dehydrated and closed by a method of heating the polyamic acid, or a method of adding a dehydrating agent and a dehydrated ring-closing catalyst to a solution obtained by dissolving the polyamic acid in an organic solvent and heating it as necessary. Of these, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure 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 0.01 to 10 mol with respect to 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.
In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. It may be used for the preparation of a liquid crystal aligning agent or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. These purification operations can be performed according to known methods.

[Solution viscosity of polymer]
The polyamic acid and the polyimide obtained as described above preferably have a solution viscosity of 20 to 800 mPa · s, and a solution of 30 to 500 mPa · s when these are each made into a solution having a concentration of 10% by weight. More preferably, it has a viscosity.
The solution viscosity (mPa · s) of the above polymer is E for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.

<Compound (B)>
The compound (B) contained in the liquid crystal alignment film of the present invention is a compound represented by the above formula (B).
R ^I in the above formula (B) is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group R ^I is, for example, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, an isobutyl group, tert- butyl group, n- pentyl radical, n -A hexyl group etc. can be mentioned.
Examples of E in the above formula (B) include the following formulas (E-1) to (E-3).

(In the above formula, “+” indicates a bond.)
The group represented by each of these, etc. can be mentioned, Among these, the group represented by the said Formula (E-1), ie, a glycidyl group, is preferable.
X in the formula (B) is a single bond, ^* —CO—, ^* —COO—CH ₂ — (the bond marked with “*” above is bonded to a nitrogen atom) or a methylene group. Are preferred.
Aro of Na Futareniru group in the formula (B) is to be 1-naphthalenyl group, it is, respectively preferred bi Feniriru group is 4-biphenylyl group.
As a compound (B) in this invention, following formula (B-1)-(B-3)

(In the formulas (B-1) to (B-3), ^RI is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
X is a single bond, ^* —CO—, ^* —COO—CH ₂ — (the bond with “*” above is bonded to a nitrogen atom) or a methylene group,
R ^II is an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms,
n1 is an integer of 0 to 5,
n2 is an integer of 0 to 7,
n3 is an integer of 0 to 4, and n4 is an integer of 0 to 5. )
The compound represented by each of these can be mentioned, At least 1 sort (s) selected from these can be used.
R ^II in the above formula is preferably a methyl group, a methoxyl group, a fluorine atom, a chlorine atom or a cyanomethyl group,
n1 is preferably an integer of 0 to 2,
n2, n3 and n4 are each preferably 0.
As a particularly preferred specific example of the compound represented by the formula (B-1), for example, the following formulas (B-1-1) to (B-1-39):

A compound represented by each of the above;
As a particularly preferable specific example of the compound represented by the formula (B-2), for example, the following formulas (B-2-1) to (B-2-10)

A compound represented by each of the above;
As a particularly preferred specific example of the compound represented by the formula (B-3), for example, the following formulas (B-3-1) and (B-3-2):

The compounds represented by each of the above can be mentioned.
R ^I in the above formula (B) is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
As the compound (B) in the present invention, a compound represented by the above formula (B-1) is preferable.
Such a compound (B) can be synthesized by appropriately combining organic chemistry methods.
The ratio of the compound (B) used in the present invention is preferably 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, and further 3 to 3 parts by weight with respect to 100 parts by weight of the polymer (A). It is preferably 30 parts by weight. By making the use ratio of the compound (B) within this range, it is possible to provide a liquid crystal alignment film that does not deteriorate in electrical characteristics even when driven continuously for a long time or has a small degree of reduction and has high long-term reliability. In addition, it is possible to obtain a liquid crystal aligning agent having high peelability (reworkability) of the formed coating film.

<Other ingredients>
Although the liquid crystal aligning agent of this invention contains the above polymers (A) and a compound (B) as an essential component, it may contain the other component as needed. Examples of such other components include functional silane compounds.
However, the liquid crystal aligning agent of the present invention preferably does not contain a compound having two or more epoxy groups in the molecule.

[Functional silane compounds]
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9- Triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxy Methyltriethoxysilane, 2-glycidoxyethyltrimeth Shishiran, 2-glycidoxyethyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl triethoxy silane and the like.
The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the polymer (A).

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is composed of the polymer (A) and the compound (B) as described above and other components optionally blended as required, preferably dissolved and contained in an organic solvent. .
Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy- 4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether , Ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. Can be mentioned. These can be used alone or in admixture of two or more.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably, when heated, a liquid crystal alignment film or a liquid crystal alignment film is formed. When the concentration is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film, while when the solid content concentration exceeds 10% by weight, In some cases, the film thickness becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
The particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). In step (1), the substrate to be used varies depending on the desired operation mode. Steps (2) and (3) are common to each operation mode.

(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface.
(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, a pair of two substrates provided with a patterned transparent conductive film is formed on each transparent conductive film forming surface, The liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method or an ink jet printing method, respectively, and then each coated surface is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. In order to obtain a patterned transparent conductive film which can be used, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a mask having a desired pattern when forming the transparent conductive film The method using can be used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.
After application of the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The firing (post-bake) temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

(1-2) On the other hand, when manufacturing an IPS type liquid crystal display element, the conductive film forming surface of the substrate provided with the comb-shaped transparent conductive film and the counter substrate provided with no conductive film The liquid crystal aligning agent of this invention is each apply | coated to one side, Then, a coating film is formed by heating each application | coating surface, and these board | substrates are used as a pair.
Regarding the material used for the substrate and the transparent conductive film, the patterning method of the transparent conductive film, the pretreatment of the substrate, the coating method of the liquid crystal aligning agent, the heating method after coating, and the preferred film thickness of the coating film to be used at this time The same as (1-1).

(2) When the liquid crystal display element to be manufactured is a VA type liquid crystal display element, the coating film formed as described above can be used as a liquid crystal alignment film as it is. It may be used after the rubbing treatment described in the above.
On the other hand, when manufacturing a liquid crystal display element other than the VA type, a rubbing treatment is performed on the coating film formed as described above to obtain a liquid crystal alignment film.
The rubbing treatment can be performed by rubbing the coating film surface formed as described above with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton in a certain direction. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.
Further, for the liquid crystal alignment film formed as described above, for example, a liquid crystal as shown in Patent Document 9 (JP-A-6-222366) or Patent Document 10 (JP-A-6-281937). Treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the alignment film with ultraviolet rays, or liquid crystal alignment as disclosed in Patent Document 11 (Japanese Patent Laid-Open No. 5-105444) A resist film is formed on a part of the film surface, then the rubbing process is performed in a direction different from the previous rubbing process, and then the resist film is removed so that the liquid crystal alignment film has different liquid crystal alignment capabilities in each region. It is possible to improve the visual field characteristics of the liquid crystal display element obtained by the above.

(3) A liquid crystal cell is prepared by preparing a pair of substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between a pair of substrates facing each other so that the surfaces of the liquid crystal alignment films face each other. To manufacture. Here, when the rubbing process is performed on the coating film, the two substrates are disposed to face each other so that the rubbing directions in the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, a pair of substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the pair of substrates are bonded using a sealing agent, and the substrate surface and the sealing agent are used. After filling and filling the liquid crystal into the partitioned cell gap, the liquid crystal cell can be manufactured by sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. After applying, for example, an ultraviolet light curable sealing material to a predetermined location on one of the pair of substrates on which the liquid crystal alignment film is formed, and then dropping the liquid crystal to predetermined locations on the liquid crystal alignment film surface The liquid crystal cell is manufactured by bonding the other substrate so that the liquid crystal alignment films face each other and spreading the liquid crystal over the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant. Can do.
Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used, and among these, a nematic liquid crystal is preferable. In the case of a VA liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, and phenylcyclohexane liquid crystal are used. It is done. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic type liquid crystal having positive dielectric anisotropy is preferable. For example, biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, biphenyl cyclohexane type A liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like is used. These liquid crystals include, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck); p Ferroelectric liquid crystals such as -decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.
As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between protective films of cellulose acetate The polarizing plate which consists of itself can be mentioned.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The solution viscosity of each polymer solution and the imidization ratio of polyimide in the synthesis examples were measured by the following methods.
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type viscometer for the solutions indicated in each synthesis example.
[Imidation rate of polyimide]
A small amount of the obtained polyimide solution was poured into pure water, was thoroughly dried under reduced pressure at room temperature and the resulting precipitate was collected, dissolved in deuterated dimethyl sulfoxide at room temperature by ¹ H tetramethylsilane as reference substance -NMR was measured. From the obtained ¹ H-NMR spectrum, the imidization ratio was determined by the formula shown by the following formula (1).
Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (1)
(In Formula (1), ^{A 1} is the peak area derived from proton of NH group appearing in the vicinity of the chemical shift 10 ppm,
A ² is the peak area derived from other protons,
α is the number ratio of other protons to one NH proton in the polymer precursor (polyamic acid). )

<Synthesis Example of Compound (B)>
Each of the following synthesis examples ensured the necessary amount in the following examples by repeating with the following scale as necessary.
Synthesis Example B-1
N-methylbenzylamine (12.1 g, 0.10 mol), methanol (100 mL) and epichlorohydrin (9.4 mL, 0.12 mol) were mixed and reacted at 80 ° C. with stirring for 6 hours. After completion of the reaction, the viscous product obtained by removing the solvent from the reaction mixture under reduced pressure was dissolved in 100 mL of tert-butanol, and then 10 mL of an aqueous potassium hydroxide solution having a concentration of 0.013 mol / L was added. Stir for hours. Next, the organic layer obtained by adding 500 mL of ethyl acetate to the reaction mixture was washed with water and then concentrated to a concentrated solution. The obtained solution was applied to a column chromatograph (filler: silica gel, developing solvent: hexane / ethyl acetate = 50/1 (volume ratio)), and the solvent was removed from the corresponding fraction, whereby compound (B-1- 14) 13.9 g (0.08 mol) of solid was obtained.
Synthesis Example B-2
In Synthesis Example B-1, compound (B) was prepared in the same manner as in Synthesis Example B-1, except that 16.3 g (0.10 mol) of N-tert-butylbenzylamine was used instead of N-methylbenzylamine. -1-20) 15.9 g (0.07 mol) of a solid was obtained.

<Polymerization example of polymer (A)>
[Polyamic acid polymerization example]
Polymerization Example PA-1
1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 109 g (0.50 mol) as tetracarboxylic dianhydride and 4,4 ′ as diamine -198 g (1.0 mol) of diaminodiphenylmethane was dissolved in a mixed solvent consisting of 230 g of N-methyl-2-pyrrolidone and 2,060 g of γ-butyrolactone, reacted at 40 ° C. for 3 hours, γ-butyrolactone 1, By adding 350 g, a solution containing 10% by weight of polyamic acid (PA-1) was obtained. The solution viscosity of this solution was 118 mPa · s.
Polymerization example PA-2
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1, .2) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine. 0 mol) is dissolved in a mixed solvent consisting of 370 g of N-methyl-2-pyrrolidone and 3,300 g of γ-butyrolactone, and reacted at 40 ° C. for 3 hours to contain 10% by weight of polyamic acid (PA-2) A solution was obtained. The solution viscosity of this solution was 154 mPa · s.

[Polyimide polymerization example]
Polymerization example PI-1
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 106 g (0.985 mol) of p-phenylenediamine and 3- (3,5-diamino as diamine 7.8 g (0.015 mol) of benzoyloxy) cholestane was dissolved in 3,042 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a solution containing 10% by weight of polyamic acid. The solution viscosity of the obtained polyamic acid solution was 181 mPa · s.
Next, 3,380 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 395 g of pyridine and 306 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone (by this operation, pyridine and acetic anhydride used for the dehydration ring-closing reaction were removed from the system. The same applies hereinafter). A solution containing 15% by weight of about 95% polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was taken, and the solution viscosity measured as a solution having a polyimide concentration of 10 wt% by adding γ-butyrolactone was 102 mPa · s.

Polymerization example PI-2
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 160 g (0.50 mol), p-phenylenediamine 94 g (0.87 mol) as diamine, 1, 25 g (0.10 mol) of 3-bis (3-aminopropyl) tetramethyldisiloxane and 9.6 g (0.015 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane and octadecylamine as monoamine. 1 g (0.030 mol) is dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain polyamic acid. To obtain a solution with. A small amount of the obtained polyamic acid solution was collected, N-methyl-2-pyrrolidone was added to make a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity was 58 mPa · s.
Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone to obtain a solution containing about 15% by weight of polyimide (PI-2) having an imidization rate of 95%. A small amount of the obtained polyimide solution was collected, and γ-butyrolactone was added thereto, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 72 mPa · s.

Polymerization example PI-3
226 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 76 g (0.80 mol) of p-phenylenediamine as diamine, cholestanyl 3,5-diaminobenzoate 53 g (0.10 mol) and 100 g (0.20 mol) of cholestanyloxy-2,4-diaminobenzene were dissolved in 1,820 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and polyamic An acid solution was obtained. A small amount of the obtained polyamic acid solution was taken, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 80 mPa · s.
Next, 4,225 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 104 g of pyridine and 134 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (PI-3) having an imidation ratio of 66%. A small amount of the obtained polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 98 mPa · s.

Polymerization example PI-4
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 87 g (0.80 mol) of p-phenylenediamine as diamine and cholestanyloxy-2,4- 99 g (0.20 mol) of diaminobenzene was dissolved in 1,848 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was taken, N-methyl-2-pyrrolidone was added to make a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity was 120 mPa · s.
Next, 3,809 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (PI-4) having an imidation ratio of 49%. A small amount of the obtained polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 155 mPa · s.

Polymerization example PI-5
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 76 g (0.70 mol) of p-phenylenediamine as diamine, 40 g of 4,4′-diaminodiphenylmethane (0.20 mol) and 50 g (0.10 mol) of cholestanyloxy-2,4-diaminobenzene were dissolved in 1,556 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid. A solution containing was obtained. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 133 mPa · s.
Next, 3,614 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (PI-5) having an imidization ratio of 46%. A small amount of the obtained polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 133 mPa · s.

<Preparation and evaluation of liquid crystal aligning agent>
[Preparation and Evaluation of TN Type Liquid Crystal Alignment Agent]
Example 1
(1) Preparation of liquid crystal aligning agent A solution containing polyamic acid (PA-1) obtained in Polymerization Example PA-1 as a polymer (A) and polyimide (PI-1) obtained in Polymerization Example PI-1 Solution containing polyamic acid (PA-1): polyimide (PI-1) = 80: 20 (weight ratio) and mixed with γ-butyrolactone (BL) and N-methyl-2-pyrrolidone. (NMP) and butyl cellosolve (BC) are added, and the compound (B-1-14) obtained in Synthesis Example B-1 as an additive corresponds to 10 parts by weight relative to 100 parts by weight of the total amount of the polymer. The amount was added and stirred sufficiently to obtain a solution having a solvent composition of BL: NMP: BC = 71: 17: 12 (weight ratio) and a solid content concentration of 3.5% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.

(2) Evaluation of reworkability of liquid crystal alignment film The liquid crystal aligning agent prepared above is applied onto a transparent conductive film made of ITO provided on one surface of a 1 mm thick glass substrate by a spinner, and 100 ° C. on a hot plate. Was pre-baked for 90 seconds to form a coating film having a thickness of about 80 nm. This operation was repeated to prepare two substrates with a coating film. Next, the two obtained substrates were stored in a dark room at 25 ° C. under a nitrogen atmosphere. After 12 hours and 72 hours from the start of storage, one substrate was taken out, immersed in a beaker containing NMP adjusted to 40 ° C. for 2 minutes, washed with ultrapure water several times, and air blown to the surface. The water drops were removed. The substrate was observed with an optical microscope and examined for the presence of a coating film residue.
At this time, even when the substrate was taken out 72 hours after the start of storage, when the coating film residue was not observed after NMP immersion, the rework property was “excellent”, and the coating film residue was observed on the substrate 72 hours later. When the film was not observed on the substrate after 12 hours, the reworkability was “good”. When the film residue was observed even after 12 hours, the reworkability was evaluated as “bad”. The reworkability of the liquid crystal aligning agent in the examples was “excellent”.

(3) Manufacture of TN type liquid crystal cell The liquid crystal aligning agent prepared above was applied with a spinner on a transparent conductive film made of ITO provided on one surface of a glass substrate having a thickness of 1 mm, and was heated on a hot plate at 80 ° C. Pre-baking was performed for 1 minute, and then heating (post-baking) was performed at 200 ° C. for 30 minutes to form a coating film having a thickness of 80 nm. 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. This 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 are overlapped with each other. The adhesive was cured by pressing together. 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.

(4) Evaluation of long-term reliability With respect to the liquid crystal cell manufactured as described above, after applying a voltage of 5 V at 70 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio after 167 milliseconds from the release of application Was measured by “VHR-1” manufactured by Toyo Corporation, and the value was defined as an initial voltage holding ratio (VH _IN , unit:%).
Next, the liquid crystal cell after the initial voltage holding ratio measurement was irradiated with light for 1,000 hours using a weather meter using a carbon arc as a light source.
With respect to the liquid crystal cell after light irradiation, the voltage holding ratio was measured again by the same method as described above, and the value was defined as the voltage holding ratio after light irradiation (VH _AF , unit:%). Here, the decrease amount of the voltage holding ratio is expressed by the following formula (2).
ΔVHR (%) = VH _IN (%) − VH _AF (%) (2)
.DELTA.VHR of this liquid crystal cell was 6.3%. Here, when the decrease amount ΔVHR of the voltage holding ratio defined as described above is less than 7%, the long-term reliability is “excellent”, and when it is 7% or more and less than 12%, the long-term reliability is “good”. When it is 12% or more, it can be said that the long-term reliability is “bad”.
Examples 2 to 19 and Comparative Examples 1 to 13
In Example 1 above, a liquid crystal aligning agent was prepared and evaluated in the same manner as in Example 1 except that the types and amounts of the polymer (A) and additives used were as shown in Table 1. “-” In the composition column of the liquid crystal aligning agent in the table indicates that the component corresponding to the column was not used.
The evaluation results are shown in Table 1.
Abbreviations of additives in Table 1 have the following meanings, respectively.
G-1: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane G-2: manufactured by Nagase ChemteX Corporation, EX-145

[Preparation and Evaluation of VA Type Liquid Crystal Alignment Agent]
Example 20
(1) Preparation of liquid crystal aligning agent As a polymer (A), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to a solution containing the polyimide (PI-3) obtained in Polymerization Example PI-3. In addition, the compound (B-1-14) obtained in Synthesis Example B-1 as an additive was added in an amount corresponding to 10 parts by weight with respect to 100 parts by weight of the polymer, and the mixture was sufficiently stirred. Was a solution having NMP: BC = 60: 40 (weight ratio) and a solid content concentration of 3.5% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
(2) Evaluation of reworkability of liquid crystal alignment film The reworkability of the liquid crystal alignment film was evaluated in the same manner as in Example 1 using the liquid crystal alignment agent prepared above.
The evaluation results are shown in Table 2.

(3) Manufacture of VA type liquid crystal cell The liquid crystal aligning agent prepared above is applied on a transparent conductive film made of ITO provided on one surface of a glass substrate having a thickness of 1 mm by a spinner. Pre-baking was performed for 1 minute, followed by heating at 210 ° C. for 30 minutes (post-baking) to form a coating film (liquid crystal alignment film) having a thickness of 80 nm. This operation was repeated to produce two (a pair) 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 are overlapped with each other. The adhesive was cured by pressing together. 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 VA type liquid crystal cell. Manufactured.
(4) Evaluation of long-term reliability The liquid crystal cell produced above was evaluated for long-term reliability in the same manner as in Example 1. However, in the case of the VA type liquid crystal cell, when the decrease amount ΔVHR of the voltage holding ratio defined in the same manner as in Example 1 is less than 2.5%, the long-term reliability is “excellent”, 2.5% or more 5 If it is less than%, the long-term reliability is “good”, and if it is 5% or more, the long-term reliability is “bad”.
The evaluation results are shown in Table 2.

Examples 21-37 and Comparative Examples 14-32
In Example 14, a liquid crystal aligning agent was prepared and evaluated in the same manner as in Example 1 except that the types and amounts of the polymer (A) and additives used were as shown in Table 2. In Examples 28 to 37 and Comparative Examples 28 to 32, two types of polyimides were used in combination as the polymer (A). “-” In the composition column of the liquid crystal aligning agent in the table indicates that the component corresponding to the column was not used.
The evaluation results are shown in Table 2.
Abbreviations of additives in Table 2 have the following meanings, respectively.
G-1: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane G-2: manufactured by Nagase ChemteX Corporation, EX-145
G-3: N, N, N ′, N′-tetraglycidyl-m-xylenediamine

Claims (5)

(A) at least one polymer selected from the group consisting of polyamic acid and polyimide, and (B) the following formula (B)

(In the formula (B), ^{R I} is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
E is a group having a 1,2-epoxy structure;
X is a single bond, ^* —COO—, ^* —CO—, ^* —COO—CH ₂ — (the bond with “*” in the above is bonded to a nitrogen atom), a methylene group or 2 to 5 carbon atoms. An alkylene group of
Aro is a phenyl group, a naphthalene group or a biphenylyl group, and these groups are an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms. May be substituted )
The liquid crystal aligning agent characterized by containing the compound represented by these. The compound (B) is represented by the following formulas (B-1) to (B-3).

(In the formulas (B-1) to (B-3), ^RI is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
X is a single bond, ^* —CO—, ^* —COO—CH ₂ — (the bond with “*” above is bonded to a nitrogen atom) or a methylene group,
R ^II is an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms,
n1 is an integer of 0 to 5,
n2 is an integer of 0 to 7,
n3 is an integer of 0 to 4, and n4 is an integer of 0 to 5. )
The liquid crystal aligning agent of Claim 1 which is at least 1 sort (s) selected from the group which consists of a compound represented by each of these. The polymer (A) is
It is selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride including 2,3,5-tricarboxycyclopentylacetic dianhydride and a diamine, and a polyimide formed by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent of Claim 1 or 2 which is an at least 1 sort (s) of polymer.   A liquid crystal aligning film formed from the liquid crystal aligning agent according to claim 1.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 4.