KR102061135B1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

(식 중, R¹은, 수소 원자이거나 또는 질소 원자에 대하여 쇄상 탄화수소기 또는 지환식 탄화수소기로 결합하는 1가의 유기기이고; R² 및 R³은, 질소 원자에 대하여 쇄상 탄화수소기, 지환식 탄화수소기 또는 *-CO-R⁴-로 결합하는 2가의 유기기이고; X¹은 질소 함유 방향족 복소환, X²는 환상 에테르기 또는 중합성 불포화기이고; m은 0 또는 1, n은 1∼3의 정수, n＝3일 때 m＝0임).(Problem) The highly reliable liquid crystal aligning film which can maintain favorable characteristic even in an excessive use environment is obtained.
(Solution means) Polymer (A), such as a polyimide, and the compound (B) represented by following formula (1) are contained in a liquid crystal aligning agent:

(In formula, R <^1> is a monovalent organic group couple | bonded with a linear hydrocarbon group or an alicyclic hydrocarbon group with respect to a nitrogen atom, or R <^2> and R <^3> are a linear hydrocarbon group and an alicyclic hydrocarbon with respect to a nitrogen atom. A divalent organic group bonded with a group or * -CO-R ^4- , X ¹ is a nitrogen-containing aromatic heterocycle, X ² is a cyclic ether group or a polymerizable unsaturated group, m is 0 or 1, and n is 1 to 1 An integer of 3 and m = 0 when n = 3).

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element, and relates to the liquid crystal display element which comprises the liquid crystal aligning agent for producing a liquid crystal aligning film, and the liquid crystal aligning film produced using the said liquid crystal aligning agent in detail. will be.

Conventionally, as the liquid crystal display element, various driving methods having different electrode structures, physical properties of liquid crystal molecules to be used, manufacturing processes, and the like have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type) ), Various liquid crystal display elements, such as FFS type and PSA type, are known. These liquid crystal display elements have a liquid crystal aligning film for orienting liquid crystal molecules. As a material of a liquid crystal aligning film, polyamic acid and polyimide are generally used from the point which various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable.

In order to obtain a liquid crystal display element with high display quality, a thing with high voltage retention in a liquid crystal aligning film, a thing with little residual charge at the time of applying a voltage, and quick relaxation of the residual charge are calculated | required. Moreover, in order to satisfy such a request, various liquid crystal aligning agents are proposed (for example, refer patent document 1, 2). Patent Literature 1 discloses that, together with polyamic acid or polyimide, a very small amount of a compound having one tertiary amino group in a molecule is contained in a liquid crystal aligning agent. Moreover, in patent document 2, it is made to contain a specific tertiary amine, such as vinylpyridine and N, N- glycidyl aniline, in a liquid crystal aligning agent with the polyimide which polyamic acid or a part of polyamic acid imidated. Is disclosed.

In recent years, the liquid crystal display element is not only used for display terminals, such as a personal computer, but is used for various uses, such as a liquid crystal television, a car navigation system, a mobile telephone, a smart phone, and an information display, for example. Along with such versatility, it is assumed that the liquid crystal display element is used in a harsher environment than before. Therefore, as a liquid crystal aligning film, the thing with the high reliability which can endure use under severe environment is calculated | required, and various liquid crystal aligning agents are proposed in order to satisfy such a request (for example, refer patent document 3 or 4). . In these patent documents 3 and 4, the liquid crystal aligning which contains the polyimide which has a carboxyl group, the primary amino group, and the primary amino group which has one nitrogen-containing aromatic heterocycle, and the primary amino group couple | bonded with the aliphatic hydrocarbon group I am disclosed.

(Patent Document 1) Japanese Patent Application Laid-Open No. 08-76128

(Patent Document 2) Japanese Patent Application Laid-Open No. 09-316200

(Patent Document 3) International Publication No. 2008/013285

(Patent Document 4) International Publication No. 2009/084665

The demand for the high performance of a liquid crystal display element is increasing, and since a favorable characteristic can be expressed even in a severe use environment as a liquid crystal aligning film, what is more favorable than a conventional thing is calculated | required.

This invention is made | formed in view of the said subject, Comprising: It makes a main object to provide the liquid crystal aligning agent for obtaining the highly reliable liquid crystal aligning film which can maintain favorable characteristics even in severe use environment.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject can be solved by using the liquid crystal aligning agent containing a specific nitrogen containing compound with polyamic acid and a polyimide, as a result of earnestly examining in order to achieve the subject of the said prior art. The present invention has been completed. Specifically, the following liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element are provided by this invention.

In one aspect, the present invention is a liquid crystal alignment containing at least one polymer (A) selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and a compound (B) represented by the following formula (1): Provides:

(In formula (1), R <^1> is a hydrogen atom or the monovalent organic group couple | bonded with a linear hydrocarbon group or an alicyclic hydrocarbon group with respect to the nitrogen atom which R <^2> and R <^3> couple | bonds, R <^2> and R <^3> are , Each independently, a chain hydrocarbon group, an alicyclic hydrocarbon group or * -CO-R ^4- (wherein R ⁴ is a divalent chain hydrocarbon group or an alicyclic hydrocarbon group to the nitrogen atom to which R ¹ is bonded; A divalent organic group bonded with a nitrogen atom to which R ¹ bonds; X ¹ is a nitrogen-containing aromatic heterocycle, X ² is a cyclic ether group or a polymerizable unsaturated group; m is 0 or 1, n is an integer of 1 to 3, provided that when m = 3, m = 0; when n is 2 or 3, a plurality of R ² and X ¹ may be the same as or different from each other; When (3-nm) = 2, some R <^3> and X <^2> may mutually be same or different).

This invention provides the liquid crystal aligning film formed using the said liquid crystal aligning agent in another aspect. Moreover, the liquid crystal display element provided with the said liquid crystal aligning film is provided.

According to the liquid crystal aligning agent of this invention, the highly reliable liquid crystal aligning film which can express favorable characteristics (for example, electrical characteristics) under severe use environment can be obtained. Moreover, since the liquid crystal display element of this invention has a liquid crystal aligning film formed using the liquid crystal aligning agent of this invention, even if it uses under severe environment, there is little fall of display quality, and it is excellent in reliability.

(Form to carry out invention)

The liquid crystal aligning agent of this invention contains at least 1 sort (s) of polymer (A) chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide, and a specific nitrogen containing compound. Below, each component contained in the liquid crystal aligning agent of this invention, and the other component arbitrarily mix | blended as needed are demonstrated.

<Polymer (A): Polyamic Acid>

Polyamic acid as a polymer (A) in this invention can be obtained by making tetracarboxylic dianhydride and diamine react.

[Tetracarboxylic dianhydride]

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in this invention, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples,

As aliphatic tetracarboxylic dianhydride, For example, 1,2,3,4-butane tetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic 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 acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraone, cyclohexanetetracarboxylic acid dianhydride and the like;

As aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride etc .; In addition to each of them, tetracarboxylic dianhydride described in JP 2010-97188 A can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesis | combination, it is preferable to contain alicyclic tetracarboxylic dianhydride from a viewpoint of transparency, the solubility to a solvent, etc. In addition, among alicyclic tetracarboxylic dianhydrides, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane- It is preferable to contain at least 1 sort (s) chosen from the group which consists of 2: 4,6: 8-2 anhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and it is 2,3,5-tree Carboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride and 1,2,3,4-cyclobutanetetracarboxylic acid It is more preferable to include at least 1 sort (s) below (it is also called specific tetracarboxylic dianhydride) chosen from the group which consists of a dianhydride.

When tetracarboxylic acid dianhydride used for synthesis | combination contains said specific tetracarboxylic dianhydride, content of the sum total of these compounds is 10 with respect to the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid. It is preferable that it is mol% or more, It is more preferable that it is 20-100 mol%, It is still more preferable that it is 50-100 mol%.

[Diamine]

Examples of the diamine used to synthesize the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples of these diamines include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl 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- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 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, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-amino Phenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholesteryl Oxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoic acid, 3,5 Diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 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-((aminope Yl) 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, 2,4-diamino-N , N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1,3-diamino-4-octadecyloxybenzene, 3- (3,5-diaminobenzoyloxy) cholestane, 3, 6-bis (4-aminobenzoyloxy) cholestane and the following formula (D-1):

(In formula (D-1), X <^I> and X <^II> are respectively independently a single bond, -O-, -COO-, or -OCO-, and R <^I> and R <^II> are respectively independently C1-C20 Is an alkanediyl group of 3, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, n is 0 or 1, provided that a and b become 0 simultaneously Is not)

Compounds represented by these;

As the diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be cited, and the diamine described in JP 2010-97188 A can be used. Can be.

The formula (D-1) from the ^{"-X I - (R I -X Ⅱ} ) n - " As the divalent group represented by, alkanediyl group having a carbon number of 1~3, * -O-, * -COO- Or * -OC ₂ H ₄ -O-, provided that the bond to which "*" is attached is combined with a diaminophenyl group.

Specific examples of the group "-C _c H _{2c +1",} for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, 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-octade A practical group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. It is preferable that two amino groups in a diaminophenyl group exist in 2, 4-position or 3, 5-position with respect to another group.

As a specific example of a compound represented by said formula (D-1), the compound etc. which are represented by each of following formula (D-1-1) (D-1-5)-are mentioned, for example.

In addition, these diamine can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the diamine used when synthesize | combining the polyamic acid in this invention contains 30 mol% or more of aromatic diamine with respect to all diamine, It is more preferable to contain 50 mol% or more, It contains 80 mol% or more More preferred.

[Molecular Weight Control Agent]

When synthesize | combining a polyamic acid, you may make it synthesize | combine the terminal-modified polymer using a suitable molecular weight modifier with tetracarboxylic dianhydride and diamine as mentioned above. By setting it as such a terminal modified polymer, the coating property (printability) of a liquid crystal aligning agent can be improved further, without impairing the effect of this invention.

As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as an acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back; As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-dodecylamine, n-octadecylamine My back; As a monoisocyanate compound, For example, phenyl isocyanate, naphthyl isocyanate, etc .; Each can be mentioned.

It is preferable to set it as 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to be used, and, as for the usage ratio of a molecular weight modifier, it is more preferable to set it as 10 weight part or less.

Synthesis of Polyamic Acid

The use ratio of tetracarboxylic dianhydride and diamine provided in the synthesis reaction of polyamic acid in this invention is a ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2-2 equivalent with respect to 1 equivalent of amino group of diamine. This is preferable and the ratio used as 0.3-1.2 equivalent is more preferable. In addition, the synthesis reaction of polyamic acid is preferably performed in an organic solvent. At this time, the reaction temperature is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. Moreover, 0.1-24 hours are preferable and, as for reaction time, 0.5-12 hours are more preferable.

Here, as an organic solvent used for reaction, a non-protic polar solvent, a phenol solvent, alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. are mentioned, for example.

Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and N-ethyl-2-pyrrolidone as aprotic polar solvents. , N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like; As the phenol solvent, for example, phenol, m-cresol, xylenol, halogenated phenol and the like;

As alcohol, For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .; As a ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methylmethoxypropionate, ethylethoxypropionate, diethyl oxalate, diethyl malonic acid, isoamylpropionate Isoamyl isobutyrate and the like;

As the ether, for example, 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, tetra Hydrofuran, diisopentyl ether and the like;

As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; As the hydrocarbon, for example, hexane, heptane, octane, benzene, toluene, xylene and the like; Each can be mentioned.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenolic solvents (first group of organic solvents), or at least one selected from the first group of organic solvents, alcohols, Preference is given to using mixtures with at least one selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). 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 relative to the total amount of the organic solvents of the first group and the organic solvents of the second group. It is below, More preferably, it is 30 weight% or less.

It is preferable that the usage-amount of organic solvent (a) sets it as the amount which the total amount (b) of tetracarboxylic dianhydride and diamine becomes 0.1-50 weight% with respect to the total amount (a + b) of a reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in a reaction solution, or after refine | purifying the isolated polyamic acid, preparation of a liquid crystal aligning agent You may provide to. In the case where the polyamic acid is subjected to the dehydration ring to be a polyimide, the reaction solution may be used as it is for the dehydration ring reaction, or after the polyamic acid contained in the reaction solution is isolated, the polyamic acid may be used for the dehydration ring reaction or the isolated polyamic acid. After purification, the reaction mixture may be subjected to a dehydration ring reaction. Isolation and purification of polyamic acid can be performed according to a well-known method.

<Polymer (A): Polyamic Acid Ester>

The polyamic acid ester as the polymer (A) in the present invention is, for example, [I] a method for synthesizing the polyamic acid obtained by the above synthesis reaction by esterifying with a hydroxyl group-containing compound or an ether compound, [II] ] The method of making tetracarboxylic acid diester dichloride and diamine react, and [III] The method of making tetracarboxylic acid diester and diamine react. In addition, the polyamic acid ester may have only a dark acid ester structure, and the partial esterified product which a dark acid structure and a dark acid ester structure coexist together may be sufficient as it.

<Polymer (A): Polyimide>

The polyimide as a polymer (A) contained in the liquid crystal aligning agent of this invention can be obtained by dehydrating and imidating the polyamic acid synthesize | combined as mentioned above.

The polyimide may be a complete imide that dehydrates and closes all of the dark acid structures possessed by polyamic acid as its precursor, or partially imides by dehydrating and ringing only part of the dark acid structure, and coexisting the dark acid structure and the imide ring structure. It may be. Since the polyimide in this invention can make voltage retention high, it is preferable that the imidation ratio is 30% or more, It is more preferable that it is 40 to 99%, It is further more preferable that it is 50 to 99% Do. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. Here, part of the imide ring may be an isoimide ring.

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

In the method of imidizing by adding a dehydrating agent and a dehydrating ring catalyst in the solution of polyamic acid, as an dehydrating agent, acid anhydrides, such as acetic anhydride, a propionic anhydride, and trifluoroacetic anhydride, can be used, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring catalyst is 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring 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 a polyimide is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring catalyst from a reaction solution, and may provide it to preparation of a liquid crystal aligning agent after isolating polyimide. You may provide it to the preparation of a liquid crystal aligning agent after refine | purifying an isolated polyimide. These purification operations can be performed according to a well-known method.

<Solution Viscosity and Weight Average Molecular Weight of Polymer (A)>

When the polyamic acid, the polyamic acid ester, and the polyimide obtained as described above have a solution having a concentration of 10% by weight, preferably have a solution viscosity of 10 to 800 mPa · s, and a solution of 15 to 500 mPa · s. It is more preferable to have a viscosity. In addition, the solution viscosity (mPa * s) of the said polymer is the density | concentration 10 prepared using the positive solvent (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.) of the said polymer. It is the value measured at 25 degreeC using the E-type rotational viscometer about the weight% polymer solution. In addition, about the polyamic acid, polyamic acid ester, and polyimide which are contained in the liquid crystal aligning agent of this invention, it is thing that the weight average molecular weight (Mw) of polystyrene conversion measured by gel permeation chromatography (GPC) is 500-100,000. It is preferable and it is more preferable that it is 1,000-50,000.

<Compound (B)>

The compound (B) contained in the liquid crystal aligning agent of this invention is a compound which has a nitrogen containing aromatic heterocycle, and is represented by the said Formula (1) specifically.

R ¹ in the formula (1) is a hydrogen atom or has a chain hydrocarbon group or an alicyclic hydrocarbon group, and is bonded to a chain hydrocarbon group or an alicyclic hydrocarbon group with respect to the nitrogen atom to which R ² and R ³ are bonded. It is a monovalent organic group. Examples of such monovalent organic groups include -O-, between carbon-carbon bonds in monovalent chain hydrocarbon groups or monovalent alicyclic hydrocarbon groups, in addition to monovalent chain hydrocarbon groups and monovalent alicyclic hydrocarbon groups. -NH-, -CO-O-, -CO-NH-, -CO-, -S-, -S (O) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) ₂ -, a monovalent group having a _{-O-Si (CH 3) 2} -O-, such as a heterocyclic group, such as an aromatic hydrocarbon group, a pyridinyl group, such as phenylene group; At least one hydrogen atom in a monovalent chain hydrocarbon group or monovalent alicyclic hydrocarbon group is substituted with an aromatic hydrocarbon group such as a fluorine atom, a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a hydroxyl group, a halogenated alkyl group or the like Monovalent groups; Etc. can be mentioned.

In addition, the chain hydrocarbon group in this specification means the saturated hydrocarbon group and unsaturated hydrocarbon group comprised only with a chain structure, without including cyclic structure in a principal chain. However, both of a linear hydrocarbon group and a branched hydrocarbon group are included. In addition, an alicyclic hydrocarbon group means a hydrocarbon group which contains only the structure of an alicyclic hydrocarbon as a ring structure, and does not contain an aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, but includes the thing which has a linear structure in one part.

As a specific example of the monovalent chain hydrocarbon group in R <^1> , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group And tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosyl group, vinyl group, propenyl group, butenyl group, pentenyl group, ethynyl group, propynyl group and the like. As specific examples of the monovalent alicyclic hydrocarbon group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexenyl group, cycloheptyl group, cyclooxe Tyl group, cyclononyl group, cyclodecyl group, cyclodecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclooctadecyl group, cycloeicosyl group, bicyclohexylyl group, decahydro Naphthyl group, norbornyl group, methyl norbornyl group, adamantyl group, etc. are mentioned.

As a monovalent organic group in R <^1> , it is preferable that it is C1-C20, It is more preferable that it is C1-C15, It is further more preferable that it is C1-C10.

The formula (1) R ² and R ³ is a chain hydrocarbon group or has an alicyclic hydrocarbon group, and R ¹ is a group-chain hydrocarbon group, alicyclic hydrocarbon group with respect to the nitrogen atom to which they bind, or * -CO-R ⁴ in However, R ⁴ is a divalent organic group bonded with a divalent chain hydrocarbon group or an alicyclic hydrocarbon group, and * represents a bond with a nitrogen atom to which R ¹ is bonded. As a bivalent organic group in R <^2> and R <^3> , a bivalent chain hydrocarbon group, a bivalent alicyclic hydrocarbon group, * -CO-R < ⁴ >-etc. are mentioned. Moreover, as said bivalent organic group, -O-, -NH-, -CO-O-, -CO-NH-,-between carbon-carbon bonds in a bivalent linear hydrocarbon group or a bivalent alicyclic hydrocarbon group CO-, -S-, -S (O) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -O-Si (CH ₃ ) ₂ -O-, phenylene group Divalent groups having a heterocyclic group such as an aromatic hydrocarbon group, pyridinylene group, etc .; At least one hydrogen atom in a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group is substituted with an aromatic hydrocarbon group such as a fluorine atom, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, a phenyl group, a hydroxyl group, a halogenated alkyl group or the like Divalent groups; It may be a back. In addition, R <^2> and R <^3> in a molecule may mutually be same or different.

Specifically, as a divalent chain hydrocarbon group in R <^2> , R <^3> and R <^4> , it is a methylene group, ethylene group, a propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, Nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, octadecylene group, ecosylene group, vinylene group, propenylene group, butenylene group, Pentenylene groups, ethynylene groups, propynylene groups and the like; As the divalent alicyclic hydrocarbon group, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclohexenylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, Cyclic decylene group, cyclododecylene group, cyclotridecylene group, cyclo tetradecylene group, cyclopentadedecylene group, cyclooctadecylene group, cyclo ethoxylene group, bicyclohexylene group, norbornylene group, Adamantylene group and the like; Each can be mentioned.

As a divalent organic group in R <^2> and R <^3> , it is preferable that it is C1-C20, It is more preferable that it is C1-C15, It is further more preferable that it is C1-C10, Especially it is C1-C5 desirable. In addition, in Formula (1), when some R <^2> exists, they may mutually be same or different, and when some R <^3> exists, they may be mutually same or different.

X ¹ in the formula (1) is a nitrogen-containing aromatic heterocycle, and the nitrogen-containing aromatic heterocycle is bonded to a nitrogen atom (a nitrogen atom to which R ¹ is bonded) via R ² . The nitrogen-containing aromatic heterocycle may be an aromatic ring containing one or more nitrogen atoms in the ring skeleton. Therefore, the ring skeleton may contain only a nitrogen atom as a hetero atom, and may contain a nitrogen atom and hetero atoms (oxygen atom, sulfur atom, etc.) other than a nitrogen atom. As a specific example of the nitrogen-containing aromatic heterocyclic ring in X ¹ , for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an indole ring, and benzoimida Sol ring, purine ring, quinoline ring, isoquinoline ring, naphthyridine ring, quinoxaline ring, phthalazine ring, triazine ring, azepine ring, diazepine ring, acridine ring, phenazine ring, phenanthroline ring, oxazole ring, thiazole ring , Carbazole ring, thiadiazole ring, benzothiazole ring, phenothiazine ring, oxadiazole ring and the like. In addition, X <^1> may be a substituent introduce | transducing into the carbon atom which comprises the ring illustrated above. As said substituent, a halogen atom, a C1-C20 monovalent organic group, etc. are mentioned, for example. Moreover, the group illustrated as the monovalent organic group of said R <^1> is mentioned as a specific example of the said monovalent organic group.

As X ¹ , among these, the ring skeleton is a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a benzoimidazole ring, a naphthyridine ring, a phthalazine ring, It is preferable that they are a quinoxaline ring, a triazine ring, an azepine ring, a diazepine ring, or a phenazine ring, and it is more preferable that they are a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring Do.

In addition, the bonding position with R <^{2> in} a nitrogen containing aromatic heterocycle is not specifically limited. For example, when the nitrogen-containing aromatic heterocycle as X ¹ is a 5-membered ring, it may be 1-position, 2-position or 3-position; in the case of 6-membered ring, 1-position, 2-position, 3-position or It can be in 4-position. When n is 2 or 3, a plurality of X ¹ independently have the above definition.

X ² in the formula (1) is a cyclic ether group or a polymerizable unsaturated group. As a cyclic ether group, it is preferable that it is an epoxy group (oxyranyl group) or an oxetanyl group, and it is more preferable that it is an epoxy group. Moreover, what is necessary is just to have a carbon-carbon double bond as a polymerizable unsaturated group, and it is preferable that they are an acryloxy group, a methacryloxy group, a vinyl group, a vinyloxy group, a maleimide group, or a styryl group specifically ,.

As a preferable specific example of a compound (B), the compound represented by following formula (1-1), the compound represented by following formula (1-2), the compound represented by following formula (1-3), etc. are mentioned:

(In formula (1-1), R <^5> is a divalent chain hydrocarbon group or alicyclic hydrocarbon group, t is 0 or 1; R <^1> and X <^1> is the same meaning as the said Formula (1), respectively.) ;

(In formula (1-2), R <^6> and R <^7> is respectively independently a bivalent chain hydrocarbon group or alicyclic hydrocarbon group, r is 1 or 2; X <^1> and X <^2> are respectively said Formula (1) The same meaning as);

(In formula (1-3), R <^8> is a divalent organic group couple | bonded with a linear hydrocarbon group or an alicyclic hydrocarbon group with respect to -CO-; R <^2> and X <^1> respectively have the same meaning as said Formula (1) being).

It is preferable that R <^1> is a hydrogen atom, a C1-C10 monovalent chain hydrocarbon group, or a C3-C10 monovalent alicyclic hydrocarbon group with respect to the compound represented by said Formula (1-1), and it is a hydrogen atom or carbon number It is more preferable that it is a 1-5 monovalent chain hydrocarbon group, and it is especially preferable that it is a hydrogen atom. It is preferable that R <^5> is a C1-C10 bivalent chain hydrocarbon group or a C3-C10 bivalent alicyclic hydrocarbon group, It is more preferable that it is a C1-C10 bivalent chain hydrocarbon group, It is C1-C5 It is especially preferable that it is a divalent chain hydrocarbon group. In addition, the preferable specific example of X <^1> can apply the description of the preferable specific example mentioned by X <^1> of said Formula (1).

t is 0 or 1, and it is preferable that it is 0 in the point which can obtain a liquid crystal aligning film with less degree of deterioration in severe use environment.

On the other hand, with respect to the compound represented by the formula (1-2), R ⁶ and R ⁷ are preferably a C 1 to C 10 divalent chain hydrocarbon group or a C 3 to C 10 divalent alicyclic hydrocarbon group. It is more preferable that it is a linear hydrocarbon group of -10, and it is especially preferable that it is a C1-C5 linear hydrocarbon group. In addition, R <^6> and R <^7> in a molecule may mutually be same or different. Specific preferred examples of X ^1, can be applied to all the preferred embodiments described in X ¹ of the formula (1). Moreover, it is preferable that X <^2> is an epoxy group, an acryloxy group, methacryloxy group, a vinyl group, a vinyloxy group, a maleimide group, or a styryl group, and it is especially preferable that it is an epoxy group.

r is 1 or 2, and it is preferable that it is 2.

Moreover, about the compound represented by said Formula (1-3), group mentioned as a specific example of R <^2> and R <^3> in said Formula (1) is mentioned as a divalent organic group in R <^8> . Preferably it is C1-C19, More preferably, it is C1-C9. It is preferable that R <^2> is a C1-C10 bivalent chain hydrocarbon group or a C3-C10 bivalent alicyclic hydrocarbon group, It is more preferable that it is a C1-C10 divalent chain hydrocarbon group, It is C1-C5 It is especially preferable that it is a divalent chain hydrocarbon group. Specific preferred examples of X ^1, can be applied to the formula (1) as a preferable specific example all of X ¹ described. In addition, some X <^1> in Formula (1-3) may mutually be same or different.

As said compound (B), the compound represented by said Formula (1-1), the compound represented by said Formula (1-2), in the point which can obtain the liquid crystal aligning film with the minimum degree of deterioration also in severe use environment, and It is preferable that it is at least 1 sort (s) chosen from the group which consists of a compound represented by said Formula (1-3). Among these, it is especially preferable that it is a compound represented by said Formula (1-1).

As a specific example of the compound (B) contained in the liquid crystal aligning agent of this invention, the compound etc. which are represented by each of following formula (ma-1)-(ma-39) are mentioned, for example. In addition, in following formula, Formula (ma-1)-(ma-19) correspond to the specific example of a compound represented by said Formula (1-1), and Formula (ma-26)-(ma-39) are said It corresponds to the specific example of a compound represented by Formula (1-2), and Formula (ma-20)-(ma-25) correspond to the compound represented by said Formula (1-3). As said compound (B), these can be used individually by 1 type or in combination of 2 or more type.

It is preferable that the compounding ratio of the said compound (B) is 0.1-30 weight part with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent. By making the compounding ratio of a compound (B) into 0.1 weight part or more, the effect like the highly reliable liquid crystal aligning film which can maintain a voltage hold ratio even in severe use environment can be acquired suitably, and it shall be 30 weight part or less It is possible to prevent the mechanical strength and the electrical characteristics of the liquid crystal alignment film from being impaired. More preferably, it is 0.5-25 weight part, More preferably, it is 1.0-20 weight part.

<Other ingredients>

The liquid crystal aligning agent of this invention may contain other components as needed. As such other components, for example, polymers other than the said polymer (A) and the compound which has at least 1 epoxy group in a molecule (except the compound corresponding to the said compound (B); Containing compound ", and a functional silane compound.

<Other polymers>

The said other polymer can be used for the improvement of a solution characteristic and an electrical property. Examples of such other polymers include polyorganosiloxanes, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. .

When adding another polymer to a liquid crystal aligning agent, it is preferable that it is 50 weight part or less with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent, It is more preferable that it is 0.1-40 weight part, It is more preferable that it is 0.1-30 weight part.

<Epoxy group-containing compound>

An epoxy group containing compound can be used in order to improve adhesiveness and electrical characteristics with the board | substrate surface in a liquid crystal aligning film. As such an epoxy group containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglyci Dilether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N' , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidylbenzylamine, N, N-diglycidylaminomethylcyclohexane, N, N-digly Cydylcyclohexylamine etc. are mentioned as a preferable thing. In addition, as an example of an epoxy group containing compound, the epoxy group containing polyorganosiloxane of international publication 2009/096598 can be used.

When adding these epoxy compounds to a liquid crystal aligning agent, 40 weight part or less is preferable with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent, and 0.1-30 weight part is more preferable.

<Functional silane compound>

The said functional silane compound can be used for the purpose of the improvement of the printability of a liquid crystal aligning agent. As such a functional silane compound, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 9-tri Methoxysilyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-methyl diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. Can.

When adding these functional silane compounds to a liquid crystal aligning agent, 2 weight part or less is preferable with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent, and 0.02-0.2 weight part is more preferable. .

In addition, as other components, the compound, antioxidant, etc. which have at least 1 oxetanyl group in a molecule | numerator can be used in addition to the above.

<Solvent>

The said polymer (A), a compound (B), and the other component arbitrarily mix | blended as needed, the liquid crystal aligning agent of this invention, Preferably melt | dissolve in an organic solvent, and are comprised.

Here, as a solvent used for preparation of the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol Methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Tate, di, and the like, propylene glycol monomethyl ether, di-isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate. These can be used individually by 1 type or in mixture of 2 or more types.

Although solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably Is in the range of 1 to 10% by weight. That is, although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably it heats, the coating film which becomes a coating film which is a liquid crystal aligning film, or a liquid crystal aligning film is formed, At this time, when solid content concentration is less than 1 weight% The film thickness of this coating film becomes too small and a favorable liquid crystal aligning film cannot be obtained. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and a favorable liquid crystal aligning film cannot be obtained, and the viscosity of a liquid crystal aligning agent increases and it becomes inferior to coating property.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable. 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 the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 20-80 degreeC. In addition, when mixing a polymer (A) and a compound (B), although the compound (B) may be added directly to the polymer solution in which the polymer (A) was melt | dissolved, a compound (B) is a suitable solvent (for example, the said polymer). After dissolving (A) in a soluble solvent), it is preferable to mix the solution and the polymer solution.

<Liquid crystal aligning film and liquid crystal display element>

The liquid crystal aligning film of this invention is formed of the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention. The drive mode to which the liquid crystal display element of the present invention is applied is not particularly limited, and can be applied to various drive modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type, and PSA type.

The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example. In the step (1), the substrate to be used differs depending on the desired driving mode. Steps (2) and (3) are common to each drive mode.

[Step (1): Formation of Coating Film]

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

(1-1) In the case of manufacturing a liquid crystal display device of TN type, STN type, VA type, MVA type or PSA type, two substrates on which a patterned transparent conductive film is formed are paired, and in each substrate The liquid crystal aligning agent of this invention is apply | coated by the offset printing method, the spin coating method, the roll coating method, or the inkjet printing method, respectively, on the formation surface of the transparent conductive film of this. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. Can be. In order to obtain a patterned transparent conductive film, for example, the pattern can be formed by forming a pattern by photo-etching after forming a patternless transparent conductive film, or by using a mask having a desired pattern when forming the transparent conductive film. . At the time of application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface and a transparent conductive film and a coating film more favorable, a functional silane compound, a functional titanium compound, etc. are previously made to the surface which forms a coating film in the board | substrate surface. The pretreatment to apply may be performed.

After application of the liquid crystal aligning agent, preliminary heating (prebaking) is preferably performed for the purpose of preventing liquid flow of the applied alignment agent. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, a firing (postbaking) step is carried out for the purpose of completely removing the solvent and for the purpose of thermally imidizing the dark acid structure present in the polymer as necessary. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. Thus, the film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(1-2) When manufacturing an IPS type or FFS type liquid crystal display element, the electrode formation surface of the board | substrate with which the electrode which consists of the transparent conductive film or metal film patterned by the comb-tooth shape is formed, and the counter substrate in which the electrode is not formed The coating film is formed by apply | coating the liquid crystal aligning agent of this invention to one surface of each, and then heating each coating surface. In this case, the material of the substrate and the transparent conductive film, the coating method, the heating conditions after the coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film are the same as in the above (1-1). . As a metal film, the film which consists of metals, such as chromium, can be used, for example.

In any of said (1-1) and (1-2), after apply | coating a liquid crystal aligning agent on a board | substrate, the coating film used as an oriented film is formed by removing an organic solvent. At this time, when the polymer contained in the liquid crystal aligning agent of this invention is a polyamic acid, a polyamic acid ester, or the imidized polymer which has an imide ring structure and a dark acid structure, dehydration ring reaction is advanced by further heating after coating film formation. It is good also as a coating film which was imidated more.

[Step (2): Rubbing Treatment]

When manufacturing a liquid crystal display element of TN type, STN type, IPS type or FFS type, the coating film formed in the said process (1) is rolled in the predetermined direction with the roll which wound the cloth which consists of fibers, such as nylon, rayon, and cotton, for example. Perform rubbing rubbing treatment. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. On the other hand, when manufacturing a VA type liquid crystal display element, although the coating film formed in the said process (1) can be used as a liquid crystal aligning film as it is, you may perform a rubbing process with respect to the said coating film. Moreover, the process which changes the pretilt angle of the one part area | region of a liquid crystal aligning film by irradiating a part of liquid crystal aligning film with ultraviolet-ray about the liquid crystal aligning film after a rubbing process, or after forming a resist film in a part of the surface of a liquid crystal aligning film, After the rubbing treatment is performed in a direction different from the rubbing treatment, the treatment may be performed to remove the resist film so that the liquid crystal alignment film has a different liquid crystal alignment ability for each region. In this case, it is possible to improve the field of view characteristic of the liquid crystal display element obtained.

When manufacturing a PSA type liquid crystal display element, although the following process (3) may be performed using the coating film formed in the said process (1) as it is, the inclination of a liquid crystal molecule is controlled and the orientation division is simplified by the method. You may perform a weak rubbing process for the purpose of performing.

[Step (3): Construction of Liquid Crystal Cell]

(3-1) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. First, the first method is a conventionally known method. In this method, first, two substrates are disposed to face each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealing agent to the substrate surface and the sealing agent. After the liquid crystal is injected and filled into the cell gap partitioned by the liquid crystal, a liquid crystal cell is produced by sealing the injection hole. The second method is a method called ODF (One Drop Fill) method. In this method, an ultraviolet curable sealing compound is apply | coated to predetermined | prescribed place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, and liquid crystal was dripped at predetermined several places on the liquid crystal aligning film surface further. Thereafter, the other substrate is bonded to face the liquid crystal alignment film. And a liquid crystal cell is manufactured by spreading a liquid crystal on the whole surface of a board | substrate, then irradiating an ultraviolet-ray to the whole surface of a board | substrate, and hardening a sealing compound. In any case, it is preferable to remove the liquid crystal filling during liquid crystal filling by gradually cooling the used liquid crystal to the temperature at which the used liquid crystal takes an isotropic phase to the liquid crystal cell produced as described above, and then gradually cooling to room temperature. .

As the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used. Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferred, and for example, sieve base liquid crystals, cyanide liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, and esters. Type liquid crystals, terphenyl type liquid crystals, biphenylcyclohexane type liquid crystals, pyrimidine type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, cuban type liquid crystals, and the like. Moreover, for these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agents as sold under the brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, may be added and used.

(3-2) In the case of manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in (3-1) except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V DC or alternating current. As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. In addition, the ultraviolet-ray of the said preferable wavelength range can be obtained by a means which uses a light source together with a filter diffraction grating etc., for example. As an irradiation amount of light, Preferably it is 1,000 J / m <2> or more and less than 200,000 J / m <2>, More preferably, it is 1,000-100,000 J / m <2>.

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate called "H film" which absorbed iodine while extending | stretching orientation of polyvinyl alcohol, the polarizing plate which sandwiched the cellulose acetate protective film with the cellulose acetate protective film, or the H film itself is mentioned. have. In addition, when the rubbing process is performed with respect to a coating film, two board | substrates are arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

The liquid crystal display element of this invention can be effectively applied to various apparatuses, For example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, smart It can be used for display devices, such as a telephone, various monitors, and a liquid crystal television.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

In the following examples and comparative examples, the imidation ratio of the polyimide in the polymer solution, the solution viscosity of the polymer solution, the weight average molecular weight and the epoxy equivalent of the polymer were measured by the following method.

[Imidation Rate of Polyimide]

The solution of polyimide was put into pure water, the obtained precipitate was dried under reduced pressure sufficiently at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the following formula (x):

Imidation ratio [%] = {(1-A ¹ ) / (A ² × α)} × 100. (x)

(In Formula (x), A ¹ is the peak area derived from the proton of the NH group which appears in the chemical shift 10 ppm vicinity, A ² is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. Number ratio of other protons to one proton of NH group).

[Solution Viscosity of Polymer Solution]

The solution viscosity [mPa * s] of a polymer solution was measured at 25 degreeC using the E-type rotational viscometer about the solution prepared at 10 weight% of polymer concentration using the predetermined solvent.

[Weight Average Molecular Weight of Polymer]

The weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

Column: Toso Co., Ltd., TSKgelGRCXLⅡ

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

[Epoxy equivalent]

Epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

Synthesis of Polymer (A)

Synthesis Example 1 Synthesis of Polyimide (PI-1)

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

Subsequently, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added to perform a dehydration ring reaction at 110 ° C for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with fresh NMP (the pyridine and acetic anhydride used for the dehydration ring reaction were removed to the outside of the system by the above operation, and the same applies hereinafter). The solution containing 26 weight% of -1) was obtained. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 10 weight% of polyimide concentration by adding NMP was 45 mPa * s.

Synthesis Example 2: Synthesis of Polyimide (PI-2)

22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 10.7 g (0.07 mol) of 3,5-diaminobenzoic acid (35DAB) as diamine, 7.35 g of cholestanyloxy-2,4-diaminobenzene (HCODA) (0.015 mol) and 6.94 g (0.015 mol) of Compound (LDA) represented by the above Formula (D-1-5) were dissolved in 190 g of NMP, and reacted at 60 ° C for 6 hours to contain 20% by weight of polyamic acid. A solution was obtained. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 80 mPa · s.

Subsequently, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 15.7 g of pyridine and 20.3 g of acetic anhydride were added, and a dehydration ring reaction was performed at 110 ° C for 4 hours. After the dehydration ring reaction, the solvent in the system was solvent-substituted with fresh NMP to obtain a solution containing 26% by weight of polyimide (PI-2) having an imidation ratio of about 80%. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 10 weight% of polyimide concentration by adding NMP was 40 mPa * s.

Synthesis Example 3: Synthesis of Polyimide (PI-3)

18.7 g (0.075 mol) of 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride (BODA) and 1,2,3 as tetracarboxylic acid dianhydride 4.90 g (0.025 mol) of, 4-cyclobutanetetracarboxylic dianhydride (CB), 10.7 g (0.07 mol) of 35DAB as diamine and 1,3-diamino-4- {4- [trans-4- (trans- 13.1 g (0.03 mol) of 4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (PBCH5DAB, the compound represented by the formula (D-1-2)) was dissolved in 190 g of NMP, and the mixture was heated at 60 ° C for 6 hours. Reaction was performed and the solution containing 20 weight% of polyamic acid was obtained. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 85 mPa · s.

Subsequently, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 9.5 g of pyridine and 12.3 g of acetic anhydride were added, and a dehydration ring reaction was performed at 110 ° C for 4 hours. After the dehydration ring reaction, the solvent in the system was solvent-substituted with fresh NMP to obtain a solution containing 26% by weight of polyimide (PI-3) having an imidization ratio of about 65%. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 10 weight% of polyimide concentration by adding NMP was 45 mPa * s.

Synthesis Example 4: Synthesis of Polyimide (PI-4)

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

Subsequently, 2,700 g of NMP were added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and a dehydration ring reaction was performed at 110 ° C for 4 hours. After the dehydration ring reaction, about 2,500 g of a solution containing 15 wt% of polyimide (PI-4) having an imidation ratio of about 95% was obtained by solvent substitution of the solvent in the system with fresh γ-butyrolactone. A small amount of this solution was added, NMP was added, and the solution viscosity measured as a solution of 10 weight% of polyimide concentration was 70 mPa * s.

Synthesis Example 5 Synthesis of Polyimide (PI-5)

22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 8.6 g (0.08 mol) of PDA as diamine, 2.0 g (0.01 mol) of 4,4'-diaminodiphenylmethane and 4,4'-diamino-2 3.2 g (0.01 mol) of, 2'-bis (trifluoromethyl) biphenyl was dissolved in 324 g of NMP, and reacted at 60 ° C for 4 hours to obtain a solution containing 10% by weight of polyamic acid.

Next, NMP360g was added to the obtained polyamic acid solution, 39.5g of pyridine and 30.6g of acetic anhydride were added, and the dehydration ring reaction was performed at 110 degreeC for 4 hours. After the dehydration ring reaction, the solvent in the system was solvent-substituted with fresh NMP to obtain a solution containing 10% by weight of polyimide (PI-5) having an imidation ratio of about 93%. The solution viscosity measured by fractional fractionation of the obtained polyimide solution was 30 mPa * s.

Synthesis Example 6 Synthesis of Polyimide (PI-6)

A polyamic acid solution was obtained in the same manner as in Synthesis Example 1 except that diamine to be used was changed to 12.2 g (0.08 mol) of 35DAB and 9.8 g (0.02 mol) of HCODA. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 80 mPa · s.

Next, imidation was performed by the method similar to the said synthesis example 1, and the solution containing 26 weight% of polyimides (PI-6) of about 65% of imidation ratios was obtained. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 10 weight% of polyimide concentration by adding NMP was 40 mPa * s.

Synthesis Example 7: Synthesis of Polyamic Acid (PA-1)

200 g (1.0 mole) of CB as tetracarboxylic dianhydride, 210 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine, a mixture of 370 g of NMP and 3,300 g of γ-butyrolactone It dissolved in a solvent and reacted at 40 degreeC for 3 hours, and obtained the solution containing 10 weight% of polyamic acid (PA-1). The solution viscosity measured by fractional fractionation of the obtained polyamic acid solution was 160 mPa * s.

Synthesis Example 8: Synthesis of Polyamic Acid (PA-2)

Tetracarboxylic dianhydride to be used is 196 g (0.9 mol) of pyromellitic dianhydride (PMDA) and 19.6 g (0.1 mol) of CB, and diamine is 0.2 mol of PDA and 4,4'- diamino diphenyl ether. A solution containing 10% by weight of polyamic acid (PA-2) was obtained in the same manner as in Synthesis Example 7 except that (DDE) was used. The solution viscosity which measured the obtained polyamic-acid solution by small aliquot was 170 mPa * s.

Synthesis Example 9: Synthesis of Polyorganosiloxane (APS-1)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine Was added and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the water after washing became neutral, and then reactive polyorganosiloxane (EPS-1) by distilling off the solvent and water under reduced pressure. ) Was obtained as a viscous transparent liquid. As a result of performing ¹ H-NMR analysis on this reactive polyorganosiloxane, the peak based on the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and the side reaction of the epoxy group was It was confirmed that it did not happen. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g / mol.

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

<Example 1>

[Preparation of liquid crystal aligning agent]

To the solution containing polyimide (PI-1) as the polymer (A), 5 parts by weight of an NMP solution of bis (3-pyridylmethyl) amine as the compound (B) was added to 100 parts by weight of the polymer in total, The solvent composition was made into the solution of NMP: BC = 50: 50 (weight ratio), and solid content concentration 6.0weight%. Liquid crystal aligning agent (S1) was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

[Production of Liquid Crystal Cell]

The liquid crystal aligning agent (S1) prepared above was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film using a liquid crystal aligning film printing machine (made by Nippon Shashin Insatsu Co., Ltd.), and on a 80 degreeC hotplate After heating (prebaking) for 1 minute and removing a solvent, it heated (postbaking) for 30 minutes on the 210 degreeC hotplate, and formed the coating film of 80 nm of average film thicknesses.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which rolled up the rayon cloth at roll rotation speed 500rpm, stage movement speed | rate 3cm / sec, hairpin indentation length 0.4mm, and provided the liquid-crystal orientation ability. . Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film, each of the said pair of board | substrates overlaps and crimps | bonds so that a liquid crystal aligning film surface may face, and an adhesive agent Was cured. Next, after filling a nematic liquid crystal (MLC-6221 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, the liquid crystal cell was produced by sealing a liquid crystal injection hole with an acryl-type photocuring adhesive.

[Evaluation of Reliability of Liquid Crystal Alignment Film]

After applying the voltage of 5V to 60 microseconds of application time and 167 milliseconds of span to the obtained liquid crystal cell, the voltage holding ratio (VHR1) after 167 milliseconds from application | release cancellation was measured. Subsequently, after leaving a liquid crystal cell in the 80 degreeC oven under LED lamp irradiation for 200 hours, it left still in room temperature and naturally cooled to room temperature. After cooling, the voltage of 5 V was applied to the liquid crystal cell at 60 microsecond application time and 167 millisecond span, and then the voltage retention rate (VHR2) 167 milliseconds after the release of the application was measured. In addition, the measurement apparatus used "VHR-1" by Toyo Technica. The change rate ((DELTA) VHR) of VHR at this time was computed by following formula (y), and the reliability of the liquid crystal aligning film was evaluated by (DELTA) VHR. The evaluation is the reliability "very good (◎)" when ΔVHR was 1% or less, the reliability "good (○)" and the case where it was 2% or less when reliability was greater than 1%. Was performed. The results are shown in Table 1 below.

[Delta] VHR [%] = {(VHR1-VHR2) / (VHR1)} x 100 Hz... (y)

In Table 1, the "addition amount" of a compound (B) shows the ratio [weight part] of the mixture with respect to a total of 100 weight part of the polymer component in a liquid crystal aligning agent. The abbreviation of the compound (B) in Table 1 has the following meanings, respectively.

Bis-AMP: bis (3-pyridylmethyl) amine (compound represented by the formula (ma-1))

Tri-AMP: tri (3-pyridylmethyl) amine (compound represented by the formula (ma-14))

Epo-AMP: a compound represented by the formula (ma-26)

Epo-AMPm: a compound represented by the formula (ma-27)

DA-AMP: a compound represented by the formula (ma-20)

DA-AEIm: a compound represented by the formula (ma-21)

NM-AMP: 3- (methylaminomethyl) pyridine

3-AMP: 3-aminomethylpyridine

<Examples 2 to 13, Comparative Examples 1 and 2>

Liquid crystal aligning agents (S2)-(S13), (R1), the same as Example 1 except having changed the kind of polymer (A) to be used, and the kind and quantity of compound (B) as Table 1 mentioned above. (R2) was prepared respectively. In addition, about each of the prepared liquid crystal aligning agent, it carried out similarly to the said Example 1, and evaluated about the reliability of a liquid crystal aligning film. The results are shown in Table 1 above. In addition, in Table 1, about Examples 7-9 which used two types of polymers as a polymer (A), the use ratio (weight%) of each polymer with respect to the total amount of the used polymer was also shown.

As shown in Table 1, in Examples 1-13 using the liquid crystal aligning agent containing a compound (B), even if it exposed after light exposure for a long time (200 hours) in 80 degreeC stress environment, there is little fall of a voltage retention rate. The reliability was good. Especially, in Examples 1-9 which used Bis-AMP or Tri-AMP as a compound (B), (DELTA) VHR was 0.6% or less, and the fall of the voltage retention by provision of optical stress and heat stress was few. On the other hand, in Comparative Examples 1 and 2 which do not contain the compound (B), the voltage holding ratio greatly decreased due to the provision of optical stress and thermal stress.

Claims (5)

At least 1 sort (s) of polymer (A) chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide, and the compound (B) represented by following formula (1),
The polymer (A) is a reaction product of tetracarboxylic dianhydride and diamine,
10 mol% or more of said tetracarboxylic dianhydride is alicyclic tetracarboxylic dianhydride,
The said compound (B) is at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (ma-1)-(ma-15) and (ma-17)-(ma-39):

(In formula (1), R ¹ is a hydrogen atom or a monovalent organic group bonded to a chain hydrocarbon group or an alicyclic hydrocarbon group with respect to the nitrogen atom to which R ² and R ³ bind; R ² and R ³ are , Each independently, a chain hydrocarbon group, an alicyclic hydrocarbon group or * -CO-R ^4- (wherein R ⁴ is a divalent chain hydrocarbon group or an alicyclic hydrocarbon group to the nitrogen atom to which R ¹ is bonded; A divalent organic group bonded with a nitrogen atom to which R ¹ bonds; X ¹ is a nitrogen-containing aromatic heterocycle, X ² is a cyclic ether group or a polymerizable unsaturated group; m is 0 or 1, n is an integer of 1 to 3, provided that when m = 3, m = 0; when n is 2 or 3, a plurality of R ² and X ¹ may be the same as or different from each other; When (3-nm) = 2, some R <^3> and X <^2> may mutually be same or different);

. The method of claim 1,
The liquid crystal aligning agent whose content rate of the said compound (B) is 0.1-30 weight part with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent. The method of claim 1,
10 mol% or more of said tetracarboxylic dianhydride is 2,3,5-tricarboxy cyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxy bicyclo [3.3.0] octane-2: 4, The liquid crystal aligning agent which is at least 1 sort (s) chosen from the group which consists of 6: 8-2 anhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-3. The liquid crystal display element provided with the liquid crystal aligning film of Claim 4.