KR20080020951A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent is provided to improve ion density and long-term reliability for electric characteristics according to the passage of time. A liquid crystal aligning agent contains a polyamic acid or a derivative thereof, an alkenyl substituted nadiimide compound, and a heterocyclic compound. The heterocyclic compound has one or two or more heterocyclic structures selected from the group consisting of oxylane, oxetane, thiirane, aziridine, oxazoline, and oxadine. The alkenyl substituted nadiimide compound has a structure represented by the formula (Ina).

Description

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

The liquid crystal which melt | dissolved in the solvent the improvement agent which combined the at least 1 sort (s) of a polyamic acid and at least 1 sort (s) of a polyamic acid derivative, and the alkenyl substituted nadiimide compound and the heterocyclic compound which has a specific heterocyclic structure in the solvent. An alignment agent, the liquid crystal aligning film formed from the said liquid crystal aligning agent, and the liquid crystal display element provided with the same.

Liquid crystal display elements are used in various liquid crystal display devices such as monitors of notebook computers and desktop computers, viewfinders of projection cameras, projection displays, and the like, and have recently been used as televisions. It is also used as an optoelectronics related element, such as an optical printer head, a high Fourier transform element, a light valve.

The liquid crystal display element is usually 1) a pair of substrates arranged to face each other, 2) an electrode formed on one or both sides of the opposing surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And a liquid crystal layer formed between the pair of substrates.

BACKGROUND ART Conventional liquid crystal display elements are mainly display elements using nematic liquid crystals, 1) twisted nematic (TN) type liquid crystal display elements twisted at 90 degrees, and 2) super twisted nematic (STN) type liquids twisted at least 180 degrees. Display element, 3) A so-called TFT (thin film transistor) type liquid crystal display element using a thin film transistor has been put into practical use. These liquid crystal display elements have a drawback in that a viewing angle that can appropriately visually recognize an image is narrow, and when viewed in an inclined direction, a decrease in luminance and contrast and inversion of luminance in halftones occur.

Recently, this problem of viewing angle includes 1) a TN-TFT type liquid crystal display element using an optical compensation film, 2) a vertical alignment and a VA (vertical alignment) type liquid crystal display element using an optical compensation film, and 3) a vertical alignment and MVA (multi domain vertical alignment) type liquid crystal display device using projection structure technology, or 4) IPS (in-plane switching) type liquid crystal display device of transverse electric field method, 5) electrically control1ed birefringence (ECB) type liquid crystal display device, 6) Improvements have been made by techniques such as optically compensated bends or optically self-compensated birefringence (OCB) type liquid crystal display elements, and the improved techniques have been put to practical use or discussed.

The development of the technology of the liquid crystal display element is achieved not only by the improvement of these drive systems and element structures, but also by the improvement of the structural member used for a liquid crystal display element. Among the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment film is one of important factors affecting the display quality of the liquid crystal display element, and the role of the liquid crystal alignment layer is increasingly important as the quality of the liquid crystal display element is improved.

A liquid crystal aligning film is prepared with a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is the solution which melt | dissolved polyamic acid or soluble polyimide in the organic solvent. After apply | coating this solution to a board | substrate, it forms into a film by means, such as a heating, and forms a polyimide oriented film. Various liquid crystal aligning agents other than polyamic acid are also examined, but most of them have not been put to practical use in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical characteristics, optical characteristics, display characteristics, and the like.

Ion density is mentioned as an important characteristic calculated | required by the liquid crystal aligning film in order to improve the display quality of a liquid crystal display element. If the ion density is low, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may cause a problem in normal gray scale display. Further, for example, even if the initial ion density is high, there is a problem that the ion density (long-term reliability) after the high temperature acceleration test is lowered.

As an attempt to solve the above problem, a number of methods have recently been proposed.

1) The polyamic-acid composition containing two or more polyamic acids from which a physical property differs for forming a liquid crystal aligning film is known (for example, refer patent document 1 and 2).

2) A varnish composition containing a polymer component containing a polyamic acid and a polyamide and a solvent is known (see Patent Document 3, for example).

3) Varnish compositions containing two or more polyamic acids and polyamides having different physical properties and a solvent are known (see Patent Document 4, for example).

4) A varnish composition containing a polymer material containing a polyamic acid or the like synthesized using a diamine compound having a specific structure is known (see Patent Document 5, for example).

5) The technique of adding a low molecular weight epoxy composition to a polyimide and a polyamic acid varnish is known (for example, refer patent document 6).

Moreover, many techniques for solving the subject including the performance improvement of a liquid crystal display element by adding an additive to a polyamic acid are proposed. As such a technique, for example, a liquid crystal aligning agent containing a curing accelerator having a polyamic acid and an oxadine structure or an oxazoline structure (see Patent Document 7, for example), and a polyamic acid and an alkenyl substituted nadiimide compound are contained. The liquid crystal aligning agent (for example, refer patent documents 8 and 9) and the liquid crystal aligning agent (for example, refer patent documents 10 and 11) containing a polyamic acid and an epoxy group containing compound are mentioned.

Moreover, many techniques for solving the subject including the performance improvement of a liquid crystal display element by adding an additive to a compound for photo-alignment are also proposed. As such a technique, the photo-alignment composition (for example, refer patent document 12) containing a dichromic molecule and the compound which has a nadiimide group as a radically polymerizable group is mentioned.

However, these prior arts cannot sufficiently solve the problem of ion density and long term reliability. For example, in patent document 7, it is thought that the said hardening accelerator evaporates, sublimes, and disintegrates in the imidation at the time of manufacturing a liquid crystal aligning film, and a hardening accelerator is produced in the liquid crystal aligning film manufactured using such a liquid crystal aligning film. The influence on the electrical characteristics of a liquid crystal aligning film is not examined.

For example, in patent document 11, adsorption of an ionic impurity is included in a subject, and the voltage retention of the manufactured liquid crystal display element is described in the Example. However, while voltage retention and ion density are related, initial voltage retention and ion density over time are not. This is considered to be because the ionic impurities are not only included in the element at the time of manufacturing the liquid crystal display element, but also occur due to decomposition of the liquid crystal, for example, in accordance with the operation of the liquid crystal display element. Therefore, although the technique of patent document 11 which adsorbs an ionic impurity is considered effective in reducing the ionic impurity contained in an element at the time of manufacture of a liquid crystal display element, it suppresses generation | occurrence | production of ionic impurity over time. There is room for review.

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-193345

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-193347

[Patent Document 3] International Publication No. 00/61684

[Patent Document 4] International Publication No. 01/000733 Pamphlet

[Patent Document 5] Japanese Patent Application Laid-Open No. 2002-162630

[Patent Document 6] Japanese Patent Application Laid-Open No. 2005-189270

[Patent Document 7] Japanese Patent Laid-Open No. 9-302225

[Patent Document 8] Japanese Patent Application Laid-Open No. 2004-341030

[Patent Document 9] Japanese Patent Laid-Open No. 9-269491

[Patent Document 10] Japanese Patent Laid-Open No. 7-234410

[Patent Document 11] Japanese Patent Application Laid-Open No. 2002-323701

[Patent Document 12] Japanese Patent Application Laid-Open No. 2003-270638

In consideration of the above situation, the liquid crystal aligning agent for a liquid crystal display device, the liquid crystal aligning film formed using the same, which improves the problem of long-term reliability with respect to the electrical properties accompanying the variation of the ion density and ion density over time, and the same The development of the equipped liquid crystal display element is desired.

The present inventors conducted research in order to solve the said subject. As a result, it contains at least one polymer selected from a polyamic acid and a derivative of this polyamic acid, and further has an alkenyl substituted nadiimide compound and an oxirane, oxetane, thiirane, aziridine, oxazoline, and oxadine structure. It has been found that a good ion density and long-term reliability can be imparted to a liquid crystal display device having a liquid crystal alignment film produced using a liquid crystal aligning agent containing a modifier containing at least one kind selected from compounds. It was completed.

Furthermore, it was found that by appropriately selecting the polyamic acid, the liquid crystal alignment film produced using the liquid crystal aligning agent can be suitably applied to liquid crystal display elements of various display driving methods.

The present invention consists of the following configurations.

[1] A liquid crystal aligning agent containing a polyamic acid or a derivative thereof, an alkenyl substituted nadiimide compound, and a heterocyclic compound,

The heterocyclic compound has a 1 or 2 or more heterocyclic structure selected from the group consisting of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxadine.

[2] The liquid crystal aligning agent according to [1], wherein the alkenyl substituted nadiimide compound is a compound represented by the following General Formula (Ina).

In general formula (Ina), R <^1> and R <^2> represents hydrogen, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, aryl, or benzyl, n is 1 The integer of -2 is shown; When n = 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbon atoms, benzyl,-(C _q H _2q ) -O _t- (C _r H _2r O ) polyoxyalkylene represented by _u -C _s H _{2s +1} (q, r, s each represents an integer of 2 to 6, t represents 0 or 1, and u represents an integer of 1 to 30). Alkyl,-(R) _v -C ₆ H ₄ -R ⁴ (v represents 0 or 1, R represents alkylene having 1 to 4 carbon atoms, R ⁴ represents hydrogen or alkyl having 1 to 4 carbon atoms) A group represented by -C ₆ H ₄ -TC ₆ H ₅ (T represents -CH _2- , -C (CH ₃ ) _2- , -CO-, -S- or -SO _2- ) A group or a group in which 1 to 3 hydrogens directly bonded to an aromatic ring of these groups can be substituted with hydroxyl groups; When n = 2, R ³ is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms,-(C _q H _2q O) _t- (C _r H _2r O) _u -C _s H _2s- polyoxyalkylene represented by (q, r, s each represents an integer of 2 to 6, t represents 0 or 1, and u represents an integer of 1 to 30), arylene having 6 to 12 carbon atoms, Represented by-(R) _v -C ₆ H ₄ -R _5- (v represents 0 or 1, and R and R ⁵ each represent alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms) -C ₆ H ₄ -TC ₆ H _4- (T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -OC ₆ H ₄ -C (CH ₃ ) _{Group represented by 2} -C ₆ H ₄ O-, -S-, or -SO _2- , or a group in which 1 to 3 hydrogens directly bonded to the aromatic ring of these groups can be substituted with hydroxyl groups. .

[3] The liquid crystal aligning agent according to [2], in which the alkenyl substituted nadiimide compound contains compounds 1 or 2 or more represented by the following structural formulas (Ina-1) to (Ina-3).

[4] The liquid crystal aligning agent according to [1] to [3], wherein the alkenyl substituted nadiimide compound is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polyamic acid or its derivative.

[5] The heterocyclic compound includes a compound having two or more heterocyclic structures, and the compound contains 1 to 100 parts by weight in total amount based on 100 parts by weight of the polyamic acid or its derivative. The liquid crystal aligning agent as described in 1]-[4].

[6] The liquid crystal aligning agent according to [1] to [5], wherein the polyamic acid or a derivative thereof is a polyamic acid obtained by reacting tetracarboxylic dianhydride as an acid component with diamine as an amine component.

[7] The acid component includes an A component and a B component, and the A component of the acid includes an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride is represented by the following structural formulas (1), (2) and (5 The liquid crystal aligning agent as described in [6] characterized by the 1 or 2 or more compound chosen from the group which consists of the following.

[8] The liquid crystal aligning agent according to [7], wherein the aromatic tetracarboxylic dianhydride is a compound of the formula (1).

[9] The liquid crystal aligning agent according to [7] or [8], wherein the B component of the acid contains any one or both of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride.

[10] The aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride may be represented by the following structural formulas (19), (23), (25), (35) to (37), (39), (44), and ( The liquid crystal aligning agent as described in [9] characterized by the above-mentioned. It is 1 or 2 or more compound chosen from the group which consists of 49).

[11] The liquid crystal aligning agent according to [10], wherein the alicyclic tetracarboxylic dianhydride is the structural formula (19).

[12] The amine component includes component A alone or both components of component A and component B. The component A of the amine is 1 or 2 selected from the group consisting of the following general formulas (I) to (VII). It is a compound represented by the above general formula, The liquid crystal aligning agent as described in [6]-[11] characterized by the above-mentioned.

In General Formula (I), A ¹ represents-(CH ₂ ) _m- . M represents the integer of 1-12 here. In General Formulas (III), (V) and (VII), A ¹ is, independently, a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, or -CONH-. , -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m -S-. Here, m represents the integer of 1-12 independently. In General Formula (VI), A ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or carbon number 1 The alkylene of -6 is shown. Further, the general formula (II) ~ cyclohexane ring, or hydrogen which is bonded to the benzene ring of (VII) are, independently, _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2 , Benzyl or 4-hydroxybenzyl.

[13] The A component of the amine is represented by the following structural formulas (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12), and (V- 33) and (VII-2) The liquid crystal aligning agent as described in [12] characterized by the 1 or 2 or more compound chosen from the group which consists of.

[14] The liquid crystal according to [12] or [13], wherein the B component of the amine is a compound represented by one or two or more general formulas selected from the group consisting of the following general formulas (VIII) to (XII). Alignment agent.

In formula (VIII), R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or — (CH ₂ ) _e −, e represents an integer of 1 to 6; R ² represents a group having a steroid skeleton, a group represented by the following general formula (XIII), an alkyl having 1 to 30 carbon atoms, or phenyl; When the alkylene and the alkyl have 2 or more carbon atoms, any of -CH ₂ -may be independently substituted with -O-, -CH = CH- or -C≡C-, provided that oxygen is continuous Hydrogen of the phenyl may be independently substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy, but when -R ¹ -R ² represents benzyl Exclude.

In addition, in formula (IX), R ³ independently represents hydrogen or methyl; R ⁴ represents hydrogen or alkyl having 1 to 30 carbon atoms; R ⁵ independently represents a single bond, -CO- or -CH _2- .

In addition, in formula (X), R ³ independently represents hydrogen or methyl; R ⁴ represents hydrogen or alkyl having 1 to 30 carbon atoms; R ⁵ independently represents a single bond, -CO- or -CH _2- ; R ⁶ and R ⁷ each independently represent hydrogen, alkyl having 1 to 30 carbon atoms, or phenyl.

In formula (XI), R ⁸ represents hydrogen or alkyl having 1 to 30 carbon atoms, and any —CH ₂ — of the above alkyl having 2 or more carbon atoms is independently —O—, —CH═CH— or — C≡C-, provided that oxygen is not continuous; R ⁹ independently represents —O— or alkylene having 1 to 6 carbon atoms; Ring A represents 1,4-phenylene or 1,4-cyclohexylene; a represents 0 or 1; b represents 0, 1 or 2; c represents 0 or 1 independently.

In general formula (XII), R ¹⁰ represents alkyl having 3 to 30 carbons or fluorinated alkyl having 3 to 30 carbons; R ¹¹ represents hydrogen, alkyl of 1 to 30 carbon atoms, or fluorinated alkyl of 1 to 30 carbon atoms; R ¹² independently represents —O— or alkylene having 1 to 6 carbon atoms; d represents O or 1 independently.

In formula (XIII), R ¹³ , R ¹⁴ And R ¹⁵ are each independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms, provided that oxygen is not continuous ) Or alkyleneoxy having 1 to 3 carbon atoms, provided that oxygen is not continuous; R ¹⁶ and R ¹⁷ each independently represent hydrogen, fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkoxyalkyl having 2 to 30 carbon atoms, fluoromethyl, difluoromethyl, trifluoromethyl, fluorome Methoxy, difluoromethoxy or trifluoromethoxy, and any —CH ₂ — in the alkyl, alkoxy and alkoxyalkyl having 2 or more carbon atoms is a group represented by difluoromethylene or the following general formula (XIV) May be substituted; Ring B and ring C each independently represent 1,4-phenylene or 1,4-cyclohexylene; f, g and h each independently represent an integer of 0 to 4; i, j and k each independently represent an integer of 0 to 3, and the sum thereof is 1 or more; 1 and m each independently represents 1 or 2.

In general formula (XIV), R <^19> , R <^20> , R <^21> and R <^22> respectively independently represent C1-C10 alkyl or phenyl, n represents the integer of 1-10.

[15] The B component of the amine is composed of the following general formulas (VIII-2), (VIII-4), (VIII-5), (VIII-6), (XI-2) and (XI-4). It is a compound represented by 1 or 2 or more general formula chosen from the group, The liquid crystal aligning agent as described in [14] characterized by the above-mentioned.

In the above general formula, R ²³ independently represents alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or alkyl having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or 1 to 20 carbon atoms. Alkyl.

[16] The liquid crystal aligning agent according to [1] to [15], wherein the polyamic acid or a derivative thereof is contained.

[17] A liquid crystal aligning agent containing a polyamic acid or a derivative thereof, an alkenyl substituted nadiimide compound, and a heterocyclic compound,

Said polyamic acid or its derivative is a polyamic acid obtained by making tetracarboxylic dianhydride as an acid component and diamine as an amine component,

The acid component includes an A component and a B component, and the A component of the acid is one or two or more selected from the group consisting of the following structural formulas (1), (2), (5) to (7) and (14) Compound, wherein the B component of the acid is selected from the group consisting of the following structural formulas (19), (23), (25), (35) to (37), (39), (44), and (49). Or two or more compounds,

The amine component includes component A alone or both components of component A and component B, and the component A of the amine includes the following structural formulas (IV-1), (IV-2), (IV-15), and (IV-16) ), (V-1) to (V-12), (V-33) and (VII-2), one or two or more compounds selected from the group consisting of the amines of the amines of the following general formula (VIII- 2), (VIII-4), (VIII-5), (VIII-6), (XI-2) and (XI-4), a compound represented by one or two or more general formulas selected from the group consisting of

The alkenyl substituted nadiimide compound includes one or two or more of the compounds represented by the following structural formulas (Ina-1) to (Ina-3),

The said heterocyclic compound is a liquid crystal aligning agent which has 1 or 2 or more heterocyclic structures chosen from the group which consists of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxadine.

In the above general formula, R ²³ independently represents alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or alkyl having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or 1 to 20 carbon atoms. Alkyl.

[18] The A component of the acid is a compound represented by the formula (1), and the B component of the acid is a compound represented by the formula (19),

The component A of the amine is one or two or more compounds represented by the structural formulas (IV-16), (V-1), (V-7) and (VII-2), and the B component of the amine is the general formula 1 or 2 or more compounds represented by (VIII-5), (XI-2) and (XI-4),

The alkenyl substituted nadiimide compound is a compound represented by the structural formula (Ina-1),

The heterocyclic compound may be 4,4'-methylenebis (N, N-diglycidylaniline), (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 2,4,6-tris (1'-aziridinyl ) -1,3,5-triazine, N, N, N ', N'-tetrakistyranylmethyl-4,4'-diaminodiphenylmethane, poly (styrene-co-2-isopropenyl -Oxazoline), and bis (3-phenyl-3,4-dihydro-2H-1,3-benzooxadin-6-yl) methane, characterized in that it comprises one or more compounds selected from the group consisting of The liquid crystal aligning agent as described in [17].

[19] A liquid crystal aligning film, which is formed by firing the liquid crystal aligning agent according to [1] to [18] in a film state.

[20] a pair of substrates opposed to each other, an electrode formed on one or both sides of the opposing surfaces of each of the pair of substrates, a liquid crystal alignment film formed on the opposing surfaces of each of the pair of substrates, and In a liquid crystal display device having a liquid crystal layer formed between a pair of substrates,

The said liquid crystal aligning film is a liquid crystal aligning film as described in [19], The liquid crystal display element characterized by the above-mentioned.

Industrial Applicability According to the present invention, it is possible to provide a liquid crystal display element of various drive systems having a high ion density and good long-term reliability over time.

The liquid crystal aligning agent of this invention is a heterocyclic ring which has 1 or 2 or more heterocyclic structures chosen from the group which consists of an alkenyl substituted nadiimide compound, an oxirane, an oxetane, a thiirane, an aziridine, an oxazoline, and an oxadine. Improvers incorporating compounds; And one or two or more polymers selected from polyamic acid and derivatives thereof; It is a composition comprising a.

<1. Alkenyl-substituted nadiimide compounds in the present invention>

The alkenyl substituted nadiimide compound which can be used by this invention is demonstrated. It is preferable that the said alkenyl substituted nadiimide compound is a compound which can be melt | dissolved in the solvent which melt | dissolves the polyamic acid or its derivative (s) and heterocyclic compound which can be used by this invention. As such an alkenyl substituted nadiimide compound, the compound represented by the following general formula (Ina) is mentioned, for example.

In general formula (Ina), R <^1> and R <^2> represents hydrogen, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, aryl, or benzyl, n is 1 The integer of -2 is shown.

In the case of the general formula (Ina), n = 1 il, R ³ is aryl, benzyl, the cycloalkyl, 6 to 12 carbon atoms, alkyl having 5-8 carbon atoms of _{1~12 - (C q H 2q)} - O _t- (C _r H _2r O) _u -C _s H _{2s +1} (q, r, s each represents an integer of 2 to 6, t represents 0 or 1, and u represents an integer of 1 to 30 Polyoxyalkylene alkyl represented by the following formula:-(R) _v -C ₆ H ₄ -R ⁴ (v represents 0 or 1, R represents alkylene having 1 to 4 carbon atoms, R ⁴ is hydrogen Or a group represented by alkyl having 1 to 4 carbon atoms, -C ₆ H ₄ -TC ₆ H ₅ (T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -S- or -SO ₂ - are 1 to 3 hydrogen bonded directly to the aromatic ring of the group, or represents a group represented by) represents a group which may be substituted with a hydroxyl group.

In the case of the general formula (Ina), n = 2 il, R ³ is a cycloalkylene, alkylene having a carbon number of 5 to 8 carbon atoms of _{2~20 - (C q H 2q O} ) t - (C r H 2r O) polyoxyalkylene represented by _u -C _s H _2s- (q, r, s each represents an integer of 2 to 6, t represents 0 or 1, and u represents an integer of 1 to 30) Arylene having 6 to 12 carbon atoms,-(R) _v -C ₆ H ₄ -R _5- (v represents 0 or 1, and R and R ⁵ are each alkylene having 1 to 4 carbon atoms or 5 to 8 carbon atoms; Represented by cycloalkylene), -C ₆ H ₄ -TC ₆ H _4- (T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -OC _{Group represented by 6} H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ O-, -S-, or -SO _2- , or 1 to 3 hydrogens directly bonded to the aromatic ring of these groups Represents a group which may be substituted with a hydroxyl group.

The alkenyl-substituted nadiimide compound is obtained by synthesizing the alkenyl-substituted nazi acid anhydride derivative and the diamine by holding it at a temperature of 80 to 220 ° C. for 0.5 to 20 hours, for example, as described in Japanese Patent No. 2729565. Compounds and commercially available compounds can be used. As a specific example of an alkenyl substituted nadiimide compound, the compound shown below is mentioned, for example.

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylmethylbicyclo [2.2.l] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-phenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-phenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2'-hydroxyethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2'-hydroxyethyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2'-hydroxyethyl) -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 3'-dihydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 3'-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (3'-hydroxy-1'-propenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxycyclohexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (3'-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (3'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {4 '-(4'-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {4 '-(4'-hydroxyphenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {4 '-(4'-hydroxyphenylisopropylidene) phenyl} -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And oligomers thereof,

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

1,2-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane,

1,2-bis {3 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane,

1,2-bis {3 '-(metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane,

Bis [2 '-{3'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether,

Bis [2 '-{3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether,

1,4-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane,

1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (arylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

1,6-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3-hydroxy-hexane,

1,12-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3,6-dihydroxy-dodecane,

1,3-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxy-cyclohexane,

1,5-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane,

1,4-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2,5-dihydroxy-benzene,

N, N'-p- (2-hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p- (2-hydroxy) xylene-bis (allylmethylcyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m- (2-hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m- (2-hydroxy) xylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p- (2,3-dihydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2'-hydroxy-phenoxy} phenyl] propane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenyl} methane,

Bis {3- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -4-hydroxyphenyl} ether,

Bis {3- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxyphenyl} sulphone,

1,1,1-tri {4 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane,

N, N ', N "-tri (ethylenemetharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) isocyanurate,

And oligomers thereof.

Furthermore, the alkenyl substituted nadiimide compound which can be used for this invention may be a compound represented by the following structural formula containing an asymmetric alkylene phenylene group.

As the alkenyl substituted nadiimide compound which can be used in the present invention, these alkenyl substituted nadiimide compounds may be used alone, or may be used as a mixture of two or more of them.

As said alkenyl substituted nadiimide compound, a following compound is mentioned as a preferable compound.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone.

As said alkenyl substituted nadiimide compound, the following compound is mentioned as a especially preferable compound.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane.

More preferable compounds as the alkenyl substituted nadiimide compound are bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by the following structural formula (Ina-1): Phenyl} methane, N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by the following structural formula (Ina-2), and And N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide represented by the following structural formula (Ina-3).

<2. Heterocyclic Compounds Usable for the Invention>

The heterocyclic compound that can be used in the present invention has one or two or more heterocyclic structures selected from the group consisting of oxirane, oxetane, thiirane, aziridine, and oxazoline. The heterocyclic compound may be one kind of compound having the heterocyclic structure or two or more kinds of compounds. The heterocyclic compound may have only one kind of heterocyclic structure in one compound, or may have two or more kinds. Moreover, although the said heterocyclic compound may have one said heterocyclic structure in one compound, it is preferable to have two or more.

In addition, the heterocyclic compound may be a polymer having a heterocyclic structure in the side chain or may be a copolymer. The polymer which has a heterocyclic structure in a side chain may be a homopolymer of the monomer which has a heterocyclic structure in a side chain, and may be a copolymer of the monomer which has a heterocyclic structure in a side chain, and the monomer which does not have a heterocyclic structure. The copolymer having a heterocyclic structure in the side chain may be a copolymer of two or more monomers having a heterocyclic structure in the side chain, or may be a copolymer of two or more monomers having a heterocyclic structure in the side chain and a monomer having no heterocyclic structure. A copolymer may be sufficient.

The heterocyclic structure has a hetero atom. Although it is not clear why the liquid crystal aligning agent containing the said heterocyclic compound is excellent in suppression of ion density and its long-term stability, the reaction of the hetero atom in the heterocyclic structure in the said heterocyclic compound, and the carbonyl group in a polyamic acid, and a liquid crystal aligning film It is thought to be related to the distribution of heterocyclic compounds in the film (universality on the surface of the film and its vicinity). Therefore, it is preferable that the heterocyclic compound has a structure in which these actions can occur, for example, a structure in which a hetero atom in the heterocyclic structure can react with a carbonyl group of the polyamic acid.

Heterocyclic compound which has oxirane mainly as a heterocyclic structure which can be used for this invention (henceforth "oxane compound"), heterocyclic compound which has oxetane mainly as heterocyclic structure (henceforth "oxetane compound" Heterocyclic compound having thiirane as the heterocyclic structure (hereinafter referred to as "thiirane compound"), heterocyclic compound having aziridine as the heterocyclic structure (hereinafter referred to as "aziridine compound") , And a heterocyclic compound having an oxazoline mainly as a heterocyclic structure (hereinafter referred to as an "oxazoline compound") are preferably soluble in a solvent in which a polyamic acid or a derivative thereof can be used in the present invention.

Examples of the oxetane compound include bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] methane and bis [(3-ethyl- 3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl- Phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [( 3-ethyl-3-oxetanylmethoxy) methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc. are mentioned. Besides these, the oligomer and polymer which have oxetanyl are mentioned.

Examples of the thiirane compound include phenylglycidyl ether, butylglycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, and N-glycidyl phthal. Mead, (nonnafluoro-N-butyl) epoxide, perfluoroethylglycidylether, epichlorohydrin, epibromohydrin, N, N-diglycidyl aniline, and 3- [2- ( Perfluorohexyl) ethoxy] -1,2-epoxypropane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl Ether, and 3- (N, N-diglycidyl) aminopropyltrime Sisilane, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane, and 3- (N-allyl-N-glycol Oxygen of the glycidyl group in the cydyl) aminopropyltrimethoxysilane, for example, J. Org. The compound etc. which substituted by sulfur and substituted the said glycidyl group by the ethylene sulfide group according to the method described in Chem., 28, 229 (1963) are mentioned.

Examples of the aziridinyl compound include 2,4,6-tris (1'-aziridinyl) -1,3,5-triazine and ω-aziridinylpyropionic acid-2,2-dihydroxymethyl-butanol. Tryester, 2,4,6-tris (2-methyl-1-aziridinyl) -1,3,5-triazine, 2,4,6-tris (2-ethyl-1-aziridinyl)- 1,3,5-triazine, 4,4'-bis (ethyleneaminocarbonylamino) diphenylmethane, bis (2-ethyl-1-aziridinyl) benzene-1,3-dicarboxylic acid amide, tris ( 2-ethyl-1-aziridinyl) benzene-1,3,5-tricarboxylic acid amide, bis (2-ethyl-1-aziridinyl) sebacic acid amide, 1,6-bis (ethyleneaminocarbonylamino) Hexane, 2,4-diethyleneureide toluene, 1,1'-carbonyl-bis-ethyleneimine, polymethylene-bis-ethyl silver urea (C2-C4), and N, N'-bis (4,6 -Diethyleneimino-1,3,5-triazin-2-yl) -hexamethylenediamine etc. are mentioned. In addition to these, oligomers and polymers having aziridinyl may also be mentioned.

Examples of oxazoline compounds include 2,2'-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, and 4-furan-2-ylmethylene-2-phenyl -4H-oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2- Oxazolin-2-yl) pyridine, 2,2'-isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline) , 2,2'-methylenebis (4-tert-butyl-2-oxazoline), 2,2'-methylenebis (4-phenyl-2-oxazoline), and the like. In addition to these, polymers and oligomers having an oxazolyl, such as epochrose (trade name, manufactured by Nippon Kogyo Co., Ltd.) may also be mentioned.

As an oxirane compound, a glycidyl ether type oxane compound, an alicyclic type oxane compound, a glycidyl ester type oxane compound, a glycidyl amine type oxane compound, a heterocyclic cyclic oxalane compound, an oxylanyl group containing acrylic compound, for example And silane oxysilane compounds.

Commercially available glycidyl ether type oxysilane compounds include, for example, epicoat 1001, epicoat 1002, epicoat 1003, epicoat 1004, epicoat 1007, epicoat 1009, and epicoat 1010 (manufactured by Chemical Epoxy). Epicoat 807 (manufactured by Chemical Cell Epoxy) and the alicyclic oxysilane compound commercially available product include, for example, CY-175, CY-177, CY-179 (manufactured by CIBA-GEIGY), ERL-4234, ERL. -4299, ERL-4221, ERL-4206 (manufactured by UCC); Examples of commercially available glycidyl ester oxysilane compounds include Shodyne 508 (manufactured by Shoden Industries Co., Ltd., Araldito CY-182, CY-192, CY-184 (CIBA-GEIGY, Epikron 200, Epiclone) 400 (manufactured by Nihon Ink Co., Ltd.), Epicoat 871, Epicoat 872 (manufactured by Chemical Cell Epoxy), ED-5661, ED-5662 (Ceranise Co.); glycidylamine Examples of the type oxysilane compound include tetraglycidyldiaminodiphenylmethane, triglycidyl-para-aminophenol, triglycidyl-meta-aminophenol, diglycidylaniline, diglycidyl toluidine, and tetraglycidyl. As a commercial product of cydyl methylenediamine, diglycidyl tribroaniline, tetraglycidyl bisaminomethylcyclohexane; and a heterocyclic oxirane compound, For example, Araldito PT810 (CIBA-GEIGY company make, Epicoat RXE-15 ( Oxidized cell epoxy products), EPITEC (products manufactured by Nippon Chemical Corporation); oxysilanyl-containing arcs It can be obtained by radically polymerizing in a catalyst together with the radically polymerizable compound which has an oxiranyl group as a ryl type compound, As a radically polymerizable compound which has an oxiranyl group, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid- 6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, N- [4- (2,3-epoxypropoxy) -3,5-dimethyl Benzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3,5-dimethylphenylpropyl] acrylamide, and the like.

Although most of the oxirane compounds exemplified herein are high molecular weights, the oxirane compounds used in the present invention are not limited depending on the molecular weight, for example, low molecular weights such as diglycidyl ether of bisphenol A or bisphenol F. You can use it. However, high molecular weight is preferable because it may elute with a liquid crystal in a low molecular weight body.

As a silane type oxane compound, it is (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) methyldimethoxysilane, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxy, for example. Silane, 5, 6-epoxyhexyl triethoxysilane, (3-glycidoxy propyl) dimethyl ethoxy silane, (3-glycidoxy propyl) methyl diethoxy silane, etc. are mentioned.

As an oxirane compound which can be used for this invention, in order to remarkably increase the effect of an oxylanyl group, you may add a promoter.

Examples of the cocatalyst include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole, isocyanuric acid and the like. Among these, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole , 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 '-(3 ", 5" -diaminotriadinyl) ethyl ] Imidazole derivatives, such as imidazole and benzimidazole, are preferable. These cocatalysts can be used individually or in combination of 2 or more types, and generally, it is preferable to use it in the ratio of 0.01-10 weight part with respect to a total amount with respect to an oxirane compound.

Although the compound represented by the following general formula (a)-(f) is mentioned as an oxadine compound which can be used for this invention, for example, It is not limited to these in particular.

In General Formulas (a), (b), (c), (d), (e) and (f), R ¹ and R ² each represent an organic group having 1 to 10 carbon atoms, and R ³ to R ⁶ are each represents a hydrogen or a hydrocarbon group of a carbon number of 1~6, X is a single bond, -O-, -S-, -SS-, -SO 2 -, -CO-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m -S- Represents the integer of 1-6.

In General Formulas (e) and (f), Y is independently a single bond, -0-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- Or alkylene having 1 to 3 carbon atoms. In General Formulas (a), (b), (c), (d), (e) and (f), hydrogen bonded to a benzene ring or a naphthalene ring is independently -F, -CH ₃ , -OH , -COOH, -SO ₃ H, or -PO ₃ H ₂ .

Moreover, the oxadine compound which can be used for this invention contains the oligomer and polymer which have an oxadine structure in a side chain, and the oligomer and polymer which have an oxadine structure in a main chain.

As an oxadine compound represented by general formula (a), the oxadine compound represented by the following structural formula and general formula is mentioned, for example.

In general formula (a-2), R <^1> has preferable C1-C30 alkyl, and its C1-C20 alkyl is more preferable.

As an oxadine compound represented by general formula (b), the oxadine compound represented by the following structural formula and general formula is mentioned, for example.

In the general formula (b-2), (b -8), (b-10), R 1 is each independently an alkyl group of 1 to 30 carbon atoms, more preferably alkyl of 1 to 20 carbon atoms.

As an oxadine compound represented by general formula (c), the oxadine compound represented by the following structural formula and general formula is mentioned, for example.

In general formulas (c-2), (c-4), (c-6), (c-8), (c-10) and (c-12), R ¹ is preferably an alkyl having 1 to 30 carbon atoms. And alkyl having 1 to 20 carbon atoms is more preferable.

As an oxadine compound represented by general formula (d), the oxadine compound represented by the following structural formula is mentioned, for example.

As an oxadine represented by general formula (e), the oxadine compound represented by the following structural formula is mentioned, for example.

As an oxadine represented by general formula (f), the oxadine compound represented by the following structural formula is mentioned, for example.

Among these, More preferably, structural formula (b-1), (c-1), (c-3), (c-5), (c-7), (c-9), (d-1) The oxadine compound represented by-(d-6), (e-3), (e-4), and (f-2)-(f-4) is mentioned.

The said oxadine compound can be manufactured by the method similar to the method of WO2004 / 009708, Unexamined-Japanese-Patent No. 11-12258, and Unexamined-Japanese-Patent No. 2004-352670, for example.

<3. Polyamic acid or derivative thereof usable in the present invention>

The polyamic acid or its derivative which can be used for this invention is a form melt | dissolved in the solvent when it is set as the liquid crystal aligning agent mentioned later, and forms the liquid crystal aligning film which has polyimide as a main component, when this liquid crystal aligning agent is used as the liquid crystal aligning film mentioned later. It is an ingredient that can be. As such a polyamic acid or its derivatives, polyamic acid, soluble polyimide, polyamic acid ester, polyamic acid amide, etc. are mentioned, for example. More specifically, 1) polyimide in which all amino and carboxy of polyamic acid are subjected to dehydration ring closure, 2) partial polyimide having been partially dehydrated and closed ring reaction, 3) polyamic acid ester in which carboxylate of polyamic acid is converted to ester, 4) Polyamic acid-polyamide copolymer obtained by reacting a part of the acid dianhydride contained in the tetracarboxylic acid dianhydride compound with organic dicarboxylic acid, and reacting 5) part or all of the polyamic acid-polyamide copolymer in a dehydration ring closure reaction. The polyamide-imide which carried out is mentioned. The polyamic acid or its derivative which can be used in the present invention may be one component of these components or two or more components.

It is preferable that the said polyamic acid or its derivative is polyamic acid obtained by making tetracarboxylic dianhydride as an acid component and diamine react as an amine component. In the present invention, such a polyamic acid can be used.

The said polyamic acid or its derivative can be obtained by reaction of tetracarboxylic dianhydride and diamine. Although 1 type, or 2 or more types of tetracarboxylic dianhydride can be used for tetracarboxylic dianhydride in this invention, one part of tetracarboxylic dianhydride may be substituted by dicarboxylic acid. Here, it is preferable that the ratio of the dicarboxylic acid with respect to tetracarboxylic dianhydride shall be 10 mol% or less.

Although 1 type, or 2 or more types of diamine can be used for the diamine in this invention, one part of diamine may be substituted by monoamine. Here, it is preferable that the ratio of the monoamine with respect to diamine shall be 10 mol% or less.

The tetracarboxylic dianhydride is optionally selected, and one or two or more compounds may be used. When using two or more tetracarboxylic dianhydrides, it is preferable to use aromatic tetracarboxylic dianhydride as an A component of an acid, and one or both of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride as a B component of an acid. 1 or 2 or more compounds can be used for these tetracarboxylic dianhydrides, respectively.

On the other hand, in order to use the polyamic acid in this invention as a component of a liquid crystal aligning agent, it is preferable that it is a form soluble in a solvent. In order to make the polyamic acid in this invention the said soluble form, it is preferable to select the tetracarboxylic dianhydride used as an acid component suitably.

Here, as said aromatic tetracarboxylic dianhydride used as an A component of an acid, the acid dianhydride represented by following structural formula (1)-(18) is mentioned concretely, for example. Among the following aromatic tetracarboxylic dianhydrides, acid dianhydrides represented by structural formulas (1), (2), (5), (6), (7) and (14) are more preferable. The pyromellitic dianhydride represented by Structural formula (1) is mentioned.

Moreover, as said aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride used as B component of an acid, the acid dianhydride represented by following structural formula (19)-(67) is mentioned concretely, for example.

Among the tetracarboxylic dianhydrides, acid dianhydrides represented by Structural Formulas (19) to (39) and (49) are more preferable, and Structural Formulas (19), (23) and (25) are more preferable. And acid dianhydrides represented by (35) to (37), (39), (44) and (49), particularly preferably 1,2,3,4- represented by Structural Formula (19). Cyclobutane tetracarboxylic dianhydride is mentioned.

In addition, in order to make the polyamic acid or its derivative (s) in this invention into polyimide soluble in a solvent, Structural formula (24), (35)-(44), (49), (50), (53) and ( It is preferable to use acid dianhydride represented by 60).

In the present invention, tetracarboxylic dianhydride represented by Structural Formulas (1) to (67) may be used alone, or two or more thereof may be used in combination. Main body using aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride (particularly preferably pyromellitic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride) The liquid crystal aligning film formed using the liquid crystal aligning agent containing the polyamic acid synthesize | combined from tetracarboxylic dianhydride in this invention can provide especially favorable ion density to the liquid crystal display element containing this.

In addition, tetracarboxylic dianhydride other than tetracarboxylic dianhydride represented by Structural Formulas (1) to (67) can also be used for the tetracarboxylic dianhydride in the present invention. Although other tetracarboxylic dianhydride is arbitrary, the tetracarboxylic dianhydride which has a side chain structure can be mentioned, for example. The liquid crystal aligning film formed using the liquid crystal aligning agent containing the polyamic acid synthesize | combined from the tetracarboxylic dianhydride in this invention using the tetracarboxylic dianhydride which has a side chain structure is free in the liquid crystal display element containing this. The tilt angle can be increased.

Although tetracarboxylic dianhydride which has a side chain structure is not specifically limited, The compound which has a steroid skeleton represented by following structural formula (68) and (69) can be used preferably in this invention.

In addition, the said other tetracarboxylic dianhydride which can be used for the tetracarboxylic dianhydride in this invention is not limited to the tetracarboxylic dianhydride which has the above-mentioned side chain structure, In addition, in the range which the objective of this invention is achieved other than that It goes without saying that tetracarboxylic dianhydride of various forms is present. These new other tetracarboxylic dianhydrides can be used individually by 1 type or in combination of 2 or more type.

In addition, a part of tetracarboxylic dianhydride used by tetracarboxylic dianhydride in this invention can be substituted by carboxylic anhydride. By substituting a part of tetracarboxylic dianhydride with carboxylic anhydride, termination of the polymerization reaction can be caused and further progress of the reaction can be suppressed, so that the molecular weight of the resulting polymer (polyamic acid) can be easily controlled. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be in a range that does not impair the effects of the present invention. However, the ratio is preferably 10 mol% or less of the total amount of the tetracarboxylic dianhydride.

As mentioned above, the polyamic acid contained in the liquid crystal aligning agent of this invention is a polymer obtained by making tetracarboxylic dianhydride and diamine react.

The diamine which can be used for this invention is arbitrarily selected, and 1 or 2 or more compounds can be used. As diamine, linear diamine may be used independently as an A component, for example, and the diamine of the said A component and the diamine which has a side chain structure as B component may be used together. When using two or more diamines, it is preferable to use the linear diamine as A component of an amine, for example, and the diamine which has a side chain structure as B component of an amine. 1 or 2 or more compounds can be used for these diamine, respectively.

Although the diamine as A component of the said amine can be arbitrarily selected if it is a diamine which does not have a side chain structure, Preferably, the diamine represented by General formula (I)-(VII) is mentioned.

In General Formula (I), A ¹ represents-(CH ₂ ) _m- . Here, m represents the integer of 1-12. In General Formulas (III), (V) and (VII), A ¹ is each independently a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, or -CONH. -, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m- S- is shown. Here, m represents the integer of 1-12 independently. In General Formula (VI), A ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or carbon number 1 The alkylene of -6 is shown. In addition, hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulas (II) to (VII) is independently -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , Benzyl or 4-hydroxybenzyl.

As diamine represented by general formula (I), the diamine represented by structural formula (I-1)-(I-4) is mentioned, for example.

As diamine represented by general formula (II), the diamine represented by structural formula (II-1) and (II-2) is mentioned, for example.

As diamine represented by general formula (III), the diamine represented by structural formula (III-1) (III-3)-is mentioned, for example.

As diamine represented by general formula (IV), the diamine represented by structural formula (IV-1) (IV-16)-is mentioned, for example.

As diamine represented by general formula (V), the diamine represented by structural formula (V-1) (V-34)-is mentioned, for example.

As diamine represented by general formula (VI), the diamine represented by structural formula (VI-1) (VI-6)-is mentioned, for example.

As diamine represented by general formula (VII), the diamine represented by structural formula (VII-1) (VII-16)-is mentioned, for example.

Among these, More preferably, Structural Formulas (IV-1) to (IV-5), (IV-15), (IV-16), (V-1) to (V-12), (V-26) , (V-27), (V-31), (V-33), (VI-1), (VI-2), (VI-6), (VII-1) to (VII-5) The diamine which becomes, and most preferably, Structural formula (IV-1), (IV-2), (IV-15), (IV-16), (V-1)-(V-12), (V -33) and diamine represented by (VII-2).

As diamine in this invention, the diamine represented by the said general formula (I)-(VII) may be used individually by 1 type, and 2 or more types may be used. The molar ratio of the diamine represented by the general formulas (I) to (VII) in the diamine in the present invention is adjusted according to the structure of the diamine represented by the selected general formulas (I) to (VII) and the desired ion density. What is necessary is just to be 1-100% in the total amount of diamine, and it is more preferable that it is 5 to 80%.

As mentioned above, although the diamine in this invention uses 1 type, or 2 or more types of diamine, especially large pretilt angles, such as a VA type liquid crystal display element, an OCB type liquid crystal display element, STN type liquid crystal display element, are calculated | required. In uses, such as, it is preferable to use diamine which has a side chain structure as B component of an amine.

In this specification, the diamine which has a side chain structure means the diamine which has a substituent (side chain) which can express predetermined | prescribed pretilt angle branched from a main chain, when the substituent which couples two amino groups is made into a main chain. That is, by using the diamine which has a side chain structure, it can react with tetracarboxylic dianhydride, and can provide the polyamic acid or polyimide (branched polyamic acid or branched polyimide) which has a side chain group with respect to a polymer main chain. The liquid crystal aligning film formed from the liquid crystal aligning agent containing the polyamic acid or polyimide which has a side chain group with respect to such a polymer main chain can increase the pretilt angle in a liquid crystal display element. This is described, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 11-193345).

Therefore, what is necessary is just to select the side chain in the diamine which has a side chain structure suitably according to the required pretilt angle. For example, the side chain is preferably a group having 3 or more carbon atoms. Specifically,

1) phenyl which may have a substituent, cyclohexylphenylene which may have a substituent, bis (cyclohexyl) phenylene which may have a substituent, or alkyl, alkenyl or alkynyl having 3 or more carbon atoms,

2) phenyloxy which may have a substituent, cyclohexyloxy which may have a substituent, bis (cyclohexyl) oxy which may have a substituent, phenylcyclohexyloxy which may have a substituent, cyclohexyl which may have a substituent Phenyloxy, alkyloxy, alkenyloxy or alkynyloxy having 3 or more carbon atoms,

3) phenylcarbonyl or alkylcarbonyl, alkenylcarbonyl or alkynylcarbonyl having 3 or more carbon atoms,

4) phenylcarbonyloxy or alkylcarbonyloxy, alkenylcarbonyloxy or alkynylcarbonyloxy having 3 or more carbon atoms,

5) Phenyloxycarbonyl which may have a substituent, cyclohexyloxycarbonyl which may have a substituent, bis (cyclohexyl) oxycarbonyl which may have a substituent, bis (cyclohexyl) phenyloxy which may have a substituent Carbonyl, cyclohexylbis (phenyl) oxycarbonyl which may have a substituent, or alkyloxycarbonyl, alkenyloxycarbonyl or alkynyloxycarbonyl having 3 or more carbon atoms,

6) phenylaminocarbonyl or alkylaminocarbonyl, alkenylaminocarbonyl or alkynylaminocarbonyl having 3 or more carbon atoms,

7) cyclic alkylene having 3 or more carbon atoms,

8) cyclohexylalkylene which may have a substituent, phenylalkylene which may have a substituent, bis (cyclohexyl) alkylene which may have a substituent, cyclohexylphenylalkylene which may have a substituent, which may have a substituent Bis (cyclohexyl) phenylalkylene, phenylalkyloxy, alkylphenyloxycarbonyl, or alkylbiphenyloxycarbonyl which may have a substituent,

9) phenyl or cyclohexyl substituted by alkyl, fluorosubstituted alkyl, or alkoxy, and

10) Alkyl, fluorosubstituted alkyl wherein two or more benzene rings or cyclohexane rings are bonded to a single bond, or are bonded through -O-, -COO-, -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms. Or a ring group substituted by alkoxy or a group having a steroid skeleton

Although these are mentioned, It is not limited to these.

Here, as a "substituent", alkyl, alkoxy, or alkoxyalkyl, etc. are mentioned.

In addition, bis (cyclohexyl) or bis (phenyl) may be interrupted by alkylene.

In addition, in this specification, when referring to "alkyl", "alkenyl", and "alkynyl", it may be linear or may be branched.

As a diamine which has a side chain structure which can be used for this invention, the diamine represented by the following general formula (VIII)-(XII) is mentioned specifically ,.

In formula (VIII), R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or — (CH ₂ ) _e −, e represents an integer of 1 to 6; R ² represents a group having a steroid skeleton, a group represented by the following general formula (XIII), alkyl having 1 to 30 carbon atoms, or phenyl; When the alkylene and the alkyl have 2 or more carbon atoms, any of -CH ₂ -may be independently substituted with -O-, -CH = CH- or -C≡C-, provided that oxygen is not continuous. And hydrogen of this phenyl may be independently substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy, except when -R ^l -R ² is benzyl. .

In formula (IX), R ³ independently represents hydrogen or methyl; R ⁴ represents hydrogen or alkyl of 1 to 3 carbon atoms; R ⁵ independently represents a single bond, -CO- or -CH _2- .

In formula (X), R ³ independently represents hydrogen or methyl; R ⁴ represents hydrogen or alkyl having 1 to 30 carbon atoms; R ⁵ independently represents a single bond, -CO- or -CH _2- ; R ⁶ and R ⁷ each independently represent hydrogen, alkyl having 1 to 30 carbon atoms, or phenyl.

In formula (XI), R ⁸ represents hydrogen or alkyl having 1 to 30 carbon atoms, and any —CH ₂ — of the above alkyl having 2 or more carbon atoms is independently —O—, —CH═CH— or C≡C. May be substituted, provided that oxygen is not continuous; R ⁹ independently represents —O— or alkylene having 1 to 6 carbon atoms; Ring A represents 1,4-phenylene or 1,4-cyclohexylene; a represents 0 or 1; b represents O, 1 or 2; c represents O or 1 independently.

In formula (XII), R ¹⁰ represents alkyl having 3 to 30 carbon atoms, or alkyl fluorinated having 3 to 30 carbon atoms; R ¹¹ represents hydrogen, alkyl of 1 to 30 carbon atoms, or alkyl fluoride of 1 to 30 carbon atoms; R ¹² independently represents —O— or alkylene having 1 to 6 carbon atoms; d represents O or 1 independently.

In formula (XIII), R ¹³ , R ¹⁴ and R ¹⁵ are each independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, 1 to 3 carbon atoms Oxyalkylene (but not oxygen) or alkyleneoxy having 1 to 3 carbon atoms, provided that oxygen is not continuous; R ¹⁶ and R ¹⁷ each independently represent hydrogen, fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkoxyalkyl having 2 to 30 carbon atoms, fluoromethyl, difluoromethyl, trifluoromethyl, fluorome Methoxy, difluoromethoxy or trifluoromethoxy, and any —CH ₂ — in the alkyl, alkoxy and alkoxyalkyl having 2 or more carbon atoms is a group represented by difluoromethylene or the following general formula (XIV) May be substituted; Ring B and ring C each independently represent 1,4-phenylene or 1,4-cyclohexylene; f, g and h each independently represent an integer of 0 to 4; i, j, and k each independently represent an integer of 0 to 3, and the sum thereof is 1 or more; 1 and m each independently represent 1 or 2.

In general formula (XIV), R <^19> , R <^20> , R <^21> and R <^22> respectively independently represent C1-C10 alkyl or phenyl, n represents the integer of l-100.

In Formula (IX), on the other hand, hydrogen bonded to carbon forming the steroid skeleton can be independently substituted with -CH ₃ .

As diamine represented by general formula (VIII), the diamine represented by the following general formula or structural formula (VIII-1) (VIII-43)-is mentioned, for example.

In general formulas (VIII-1) to (VIII-11), R ²³ preferably represents alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, and preferably alkyl having 5 to 25 carbon atoms or alkoxy having 5 to 25 carbon atoms. More preferably. In addition, R ²⁴ preferably represents alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, more preferably alkyl having 3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms.

In general formulas (VIII-12) to (VIII-15), R ²⁵ preferably represents alkyl having 4 to 30 carbon atoms, and more preferably represents alkyl having 6 to ²⁵ carbon atoms. In General Formulas (VIII-16) and (VIII-17), R ²⁶ preferably represents alkyl having 6 to 30 carbon atoms, and more preferably represents alkyl having 8 to 25 carbon atoms.

In General Formulas (VIII-18) to (VIII-37), R ²⁷ preferably represents alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and alkyl having 3 to 25 carbon atoms or 3 to 25 carbon atoms. It is more preferable to represent alkoxy. In addition, R ²⁸ are, -H, -F, alkoxy, -CN alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF and more preferably represents a ₂ or -OCF _3, carbon number of 3 to It is more preferable to represent 25 alkyl or alkoxy having 3 to 25 carbon atoms.

Among these, Preferably, the diamine represented by general formula (VIII-1) (VIII-11)-is mentioned. More preferably, the diamine represented by general formula (VIII-2), (VIII-4), (VIII-5), and (VIII-6) is mentioned.

In the general formula (IX), one of the two "NH ₂ -Ph-R ⁵ -O-" is preferably bonded to the 3 position of the steroid skeleton, and the other is bonded to the 6 position. Moreover, it is preferable that two amino groups are respectively couple | bonded with the phenyl ring carbon, and are couple | bonded with meta or para with respect to the bonding position of R <^5> .

As diamine represented by general formula (IX), the diamine represented by structural formula (IX-1) (IX-4)-is mentioned, for example.

In the general formula (X), two "NH _2- (R ^7- ) Ph-R ⁵ -O-" are each bonded to a carbon of a phenyl ring, but preferably to a carbon to which a steroid skeleton is bonded. It is bound to carbon of meta or para. Moreover, although two amino groups are each couple | bonded with the phenyl ring carbon, it is preferable that they are couple | bonded with meta or para with respect to R <^5> .

As diamine represented by general formula (X), the diamine represented by structural formula (X-1)-(X-8) is mentioned, for example.

In the said general formula (XI), although two amino groups are each couple | bonded with the carbon of a phenyl ring, it is preferable that they are couple | bonded with meta or para with respect to R <^9> .

As a diamine represented by general formula (XI), the diamine represented by general formula (XI-1) (XI-8)-is mentioned, for example.

In general formulas (XI-1) to (XI-3), R ²⁹ preferably represents -H and an alkyl group having 1 to 30 carbon atoms, and in general formulas (XI-4) to (XI-8), R ³⁰ It is more preferable to represent -H and a C1-C20 alkyl group.

In the said general formula (XII), although two amino groups are each couple | bonded with the carbon of a phenyl ring, it is preferable that they are couple | bonded with meta or para with respect to R <^12> .

As diamine represented by general formula (XII), the diamine represented by general formula (XII-1) (XII-3)-is mentioned, for example.

In General Formulas (XII-1) to (XII-3), R ³¹ preferably represents an alkyl group having 6 to 20 carbon atoms, and R ³² preferably represents -H or an alkyl group having 1 to 10 carbon atoms.

As diamine in this invention, the diamine represented by the said general formula (VIII)-(XII) may be used individually by 1 type, and 2 or more types may be used. What is necessary is just to adjust the molar ratio of the diamine which has a side chain structure in diamine in this invention according to the structure of the diamine which has a selected side chain structure, and a desired pretilt angle, It is preferable that it is 1 to 100%, It is 10 to 100 It is more preferable that it is%.

As the diamine in the present invention, diamines other than diamines represented by general formulas (I) to (VII) and side chain structures represented by general formulas (VIII) to (XII) can be used. . Such other diamines are optional, but for example, naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, or siloxane-based diamines having a siloxane bond, or other than general formulas (VIII) to (XII) The diamine which has a side chain structure is mentioned.

Although a siloxane diamine is not specifically limited, The compound represented by the following general formula (XV) can be used suitably as a diamine in this invention.

In formula (XV), R ³³ and R ³⁴ each independently represent alkyl or phenyl having 1 to 3 carbon atoms, and A ³ independently represent methylene, phenylene or alkyl substituted phenylene. 1 represents the integer of 1-6, m represents the integer of 1-10.

In addition, although other diamine is not specifically limited to the said siloxane type diamine, For example, the compound represented by following General formula (1 ')-(8') can be used suitably as a diamine in this invention.

In General Formulas (1 ') to (8'), R ³⁵ and R ³⁶ each independently represent an alkyl group having 3 to 30 carbon atoms.

In addition, the said other diamine other than general formula (I)-(XII) used as the diamine in this invention is not limited only to the said siloxane-based diamine, etc., In addition, in the range in which the objective of this invention is achieved, various other It goes without saying that the diamine in the form is present. In addition, the said other diamine can be used individually by 1 type or in combination of 2 or more type.

The diamine in this invention can provide a suitable pretilt angle to the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention by selecting the kind of diamine and its combination suitably.

In the case of a VA type liquid crystal display device, a large pretilt angle of about 80 to 90 degrees is obtained. In the case of an OCB type liquid crystal display device, a pretilt angle of about 7 to 20 degrees is a TN type liquid crystal display device or an STN type liquid crystal display device. In the case of, a pretilt angle of about 3 to 10 degrees and a small pretilt angle of about 0 to 3 degrees are often required in the case of an IPS type liquid crystal display element. Therefore, the liquid crystal aligning agent of this invention which can adjust the pretilt angle suitably using the diamine which has a side chain structure can be applied to the liquid crystal display element of arbitrary types.

As mentioned above, a part of diamine used as the diamine in this invention can be substituted by monoamine. By substituting a part of the diamine with a monoamine, termination of the polymerization reaction can be caused and further progress of the reaction can be suppressed, so that the molecular weight of the polymer (polyamic acid) obtained can be easily controlled. The ratio of the monoamine to the diamine may be in a range that does not impair the effects of the present invention. However, the ratio of the monoamine to the diamine is preferably 10 mol% or less of the total amount of the amine.

The polyamic acid or its derivative in this invention can have arbitrary weight average molecular weights. Although the weight average molecular weight of the said polyamic acid or its derivatives is not specifically limited, When used as a component of a liquid crystal aligning agent, it is 5 * 10 <^3>. It is preferable that it is more than 1x10 <^4> It is more preferable that it is above. 5 × 10 ³ The polyamic acid or its derivative having the above weight average molecular weight does not evaporate in the step of baking the liquid crystal aligning film, and has preferable physical properties as a component of the liquid crystal aligning agent.

Here, the weight average molecular weight of a polyamic acid or its derivative is measured by the gel permeation chromatography (GPC) method. For example, the obtained polyamic acid or derivatives thereof are diluted with dimethylformamide (DMF) so that the concentration of the polyamic acid or derivatives thereof is about 1% by weight, and using chromatography pack C-R7A (manufactured by 島 津 製作 所), DMF is measured by gel permeation chromatography analysis (GPC) as a developing solvent and determined by polystyrene conversion. In addition, in order to perform GPC measurement such as polyamic acid or polyacrylic acid with good accuracy, a developing solvent in which inorganic acids such as phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid, and inorganic salts such as lithium bromide and lithium chloride are dissolved in a DMF solvent may be prepared. Can be.

The polyamic acid or its derivative in this invention can be manufactured using a well-known method. For example, in the reaction vessel provided with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer and a condenser, one kind or two or more kinds of diamines represented by general formulas (I) to (XII), and other diamines as the case may be One or two or more diamines selected from the group, and a predetermined amount of monoamine are injected as necessary.

Subsequently, a solvent (for example, N-methyl-2-pyrrolidone, dimethylformamide, etc.), which is an amide polar solvent, and one or two or more kinds of tetracarboxylic dianhydride, and carboxylic anhydride are added as necessary. do. At this time, the total amount of tetracarboxylic acid dianhydride is preferably approximately equal to the total number of moles of diamine (molar ratio of 0.9 to 1.1).

The solution of polyamic acid can be obtained by making it react for 1 to 48 hours at the temperature of 0-70 degreeC under stirring. Moreover, polyamic acid with a small molecular weight can also be obtained by heating and raising reaction temperature (for example, 50-80 degreeC).

The polyamic acid in the present invention can be identified by precipitating with a large amount of poor solvent, completely separating the solid content and the solvent by filtration or the like, and analyzing by IR and NMR. Moreover, the monomer used can be identified by decomposing | dissolving a solid polyamic acid with strong alkaline aqueous solution, such as KOH and NaOH, extracting with an organic solvent, and analyzing by GC, HPLC, or GC-MS.

The obtained polyamic acid solution can be diluted with a solvent and used in order to adjust to a desired viscosity.

In addition, when making the polyamic acid in this invention the soluble polyimide which is a polyamic acid derivative, the polyamic acid solution is acid anhydrides, such as acetic anhydride, a pyrophytic anhydride, and trifluoroacetic anhydride which are dehydrating agents, and dehydration ring closure. It can obtain by imidation reaction at the temperature of 20-150 degreeC with tertiary amine, such as triethylamine, a pyridine, and a collidine which are catalysts.

Alternatively, the polyamic acid is precipitated using a large amount of poor solvent (alcohol solvent such as methanol, ethanol, isopropanol or glycol solvent) as a polyamic acid solution, and the precipitated polyamic acid is dissolved in a solvent such as toluene or xylene. It can also be obtained by imidation reaction at the temperature of 20-150 degreeC with the same dehydrating agent and dehydration ring-closure catalyst.

In the said imidation reaction, it is preferable that the ratio of a dehydrating agent and a dehydration ring-closure catalyst is 0.1-10 (molar ratio). It is preferable that the total usage-amount of both is 1.5-10 times mole with respect to the total molar amount of the acid dianhydride contained in the tetracarboxylic dianhydride to be used. By adjusting the dehydrating agent, catalyst amount, reaction temperature, and reaction time of such chemical imidation, the degree of imidation can be controlled and a partial polyimide can be obtained.

The obtained polyimide can also be used as a liquid crystal aligning agent, separately from a solvent, re-dissolving it in the solvent mentioned later in combination with the improving agent which combined at least 1 sort (s) chosen from the said alkenyl substituted nadiimide compound and the said heterocyclic compound, Or you may use as a liquid crystal aligning agent, adding the said improvement agent, without separating with a solvent.

As described above, part of the acid dianhydride used as the tetracarboxylic dianhydride in the present invention may be substituted with an organic dicarboxylic acid. When the polyamic acid of the present invention is prepared using organic dicarboxylic acid and tetracarboxylic dianhydride, a polyamic acid-polyamide copolymer can be obtained. Here, although the ratio of the organic dicarboxylic acid with respect to tetracarboxylic dianhydride should just be a range which does not impair the effect of this invention, as a reference | standard, it is preferable to set it as 10 mol% or less.

In addition, polyamideimide can be prepared by chemically imidating the polyamic acid-polyamide copolymer.

<4. Liquid crystal aligning agent of this invention>

The liquid crystal aligning agent of this invention contains the said alkenyl substituted nadiimide compound, the said heterocyclic compound, and the polyamic acid of this invention mentioned above, or its derivative (s). The liquid crystal aligning agent of this invention may further contain a solvent from a viewpoint of adjustment of physical properties, such as a viscosity, ease of handling, simplification of a process, etc., and may also contain various additives contained in a normal liquid crystal aligning agent. .

It is preferable that it is 1-100 weight part with a total amount per 100 weight part of polyamic acid or its derivative in a liquid crystal aligning agent, and, as for the content rate of the alkenyl substituted nadiimide compound of the improving agent in the said liquid crystal aligning agent, it is 1-70 weight part It is more preferable, and when it is used as a liquid crystal display element, what is 1-50 weight part is further more preferable, since electric characteristic is stabilized in a long term.

It is preferable that it is 1-100 weight part in total amount, and, as for the ratio of the said heterocyclic compound of the improving agent in the said liquid crystal aligning agent in this invention in 100 weight part of polyamic acid or its derivatives, it is more preferable that it is 1-70 weight part. In addition, when it is used as a liquid crystal display element, what is 1-50 weight part is more preferable, since electric characteristic is stabilized in a long term.

Content in the liquid crystal aligning agent of the said heterocyclic structure in the said heterocyclic compound changes with kinds of heterocyclic structure. The relationship between the reduction of the ion density and the suppression of the increase over time and the heterocyclic compound in the case of the liquid crystal display device is not clear as described above, but the amount of the heterocyclic structure and the expression of the effect are related. I think there is.

It is preferable that content of the oxirane compound in a liquid crystal aligning agent is 0.1 to 80 weight% with respect to a polyamic acid or its derivative, when converting the oxirane structure in an oxane compound into oxirane. It is preferable that content of the oxetane compound in a liquid crystal aligning agent is 0.1 to 80 weight% with respect to a polyamic acid or its derivative, when oxetane structure in an oxetane compound is converted into oxetane. Moreover, it is preferable that content of the thiirane compound in a liquid crystal aligning agent is 0.1 to 80 weight% with respect to a polyamic acid or its derivative, when converting the thiirane structure in a thiirane compound into thiirane. Moreover, when content of the aziridine compound in a liquid crystal aligning agent is converted into the aziridine structure in an aziridine compound, it is preferable that it is 0.1 to 80 weight% with respect to a polyamic acid or its derivative (s). Moreover, when content of the oxazoline compound in a liquid crystal aligning agent converts the oxazoline structure in an oxazoline compound into oxazoline, it is preferable that it is 0.1-80 weight% with respect to a polyamic acid or its derivative. Moreover, it is preferable that content of the oxadine compound in a liquid crystal aligning agent is 0.1 to 80 weight% with respect to a polyamic acid or its derivative, when converting the oxadine structure in an oxadine compound into an oxadine.

On the other hand, when 2 or more types of heterocyclic structures are contained in a heterocyclic compound, content of the heterocyclic structure in a liquid crystal aligning agent is calculated | required according to the ratio of each heterocyclic structure in a heterocyclic compound.

The ratio of the heterocyclic compound to the alkenyl-substituted nadiimide compound in the liquid crystal aligning agent is preferable in order to suppress the decrease of the ion density and the increase of the ion density over time when the liquid crystal display device is used. Preferably it is 0.1-10 by weight ratio, More preferably, it is 0.5-5.

As the polyamic acid or its derivative in the present invention, the above-described polyamic acid or its derivative can be used. For example, if it is a polyamic acid, the polyamic acid obtained by making the A component or B component of the said acid, and the A component or B component of the said amine react, the A component or B component of the said acid, and the A component or B component of the said amine Polyamic acid obtained by reacting, A component or B component of the acid, A component and B component of the amine, and A component and B component of the acid and A component and B component of the amine The polyamic acid obtained by making it carry out, etc. are mentioned.

The content rate of the polyamic acid or its derivative in the liquid crystal aligning agent of this invention can be suitably selected according to the coating method to the board | substrate of a liquid crystal aligning agent. For example, the content rate of the polyamic acid or its derivative in the liquid crystal aligning agent used in the printing machine (including offset printing machine or inkjet printing machine, abbreviated as printing machine hereafter) which can be used in the manufacturing process of a normal liquid crystal display element, It is preferable that it is 0.5-30 weight% in total amount, More preferably, it is preferable that it is 1-15 weight% in total amount, but it adjusts suitably according to the relationship with the viscosity of a liquid crystal aligning agent.

The solvent which can be used for this invention includes the solvent normally used for the manufacturing process or use of polymer components, such as a polyamic acid, soluble polyimide, and polyamideimide, and can be suitably selected according to a use purpose. It is preferable that the said solvent is a mixed solvent containing 1) the aprotic polar organic solvent which is soluble with respect to a polyamic acid and soluble polyimide, and 2) the solvent aimed at improving a coating property by changing surface tension.

Illustrative of these solvents are as follows.

1) Aprotic polar organic solvent (hereinafter referred to as aprotic polar organic solvent) which is a good solvent for polyamic acid or soluble polyimide: N-methyl-2-pyrrolidone, dimethylimidazolidinone, N -Methyl caprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone and γ-valerolactone. Among these, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, (gamma) -butyrolactone, (gamma) -valerolactone, etc. are more preferably illustrated.

2) Solvents for the purpose of improving the coating property by changing the surface tension (hereinafter, other solvents): for example, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isopron, ethylene glycol mono Ethylene glycol monoalkyl ethers such as butyl ether, diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, and propylene glycol monobutyl ether such as propylene glycol monobutyl ether Dipropylene glycol monoalkyl ethers, such as dialkyl malonate, such as alkyl ether and diethyl malonate, and dipropylene glycol monomethyl ether, and ester compounds, such as these acetates. Among these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether and the like are more preferably exemplified.

The kind and ratio of an aprotic polar solvent and other solvent can be suitably set in consideration of the printability, coating property, solubility, storage stability, etc. of a liquid crystal aligning agent. Aprotic polar solvents tend to have better solubility and storage stability than other solvents, and other solvents tend to have excellent printability and applicability.

As mentioned above, the liquid crystal aligning agent of this invention may contain various additives. As various additives, high molecular compounds other than a polyamic acid or its derivatives, or a low molecular weight compound can be selected and used according to each objective.

For example, the polymer compound soluble in an organic solvent may be used as an additive, and by adding these, electrical properties and orientation of the formed liquid crystal alignment film can be controlled. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, silicone-modified polyester and the like.

Moreover, as an additive of a low molecular weight compound, it is 1) surfactant in order to improve applicability, 2) antistatic agent in order to improve antistatic property, and 3) in order to improve adhesiveness and rubbing resistance with a board | substrate. The imidation catalyst can be used when a silane coupling agent and a titanium-type coupling agent are going to advance 4) imidation at low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3-aminoprop Lofilmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-glycidoxyoxypropyltrimethoxysilane, 3-glycidoxyoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (Triethoxysilyl) -1-propylamine, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine Etc. can be mentioned.

Examples of the imidation catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline and hydroxy substituted aniline; Pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. It is preferable to add catalysts, such as cyclic amines. In particular, N, N- dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, isoquinoline, etc. are mentioned.

The addition amount of a silane coupling agent is 0 to 10 weight% of the total weight of a polyamic acid or its derivative normally, and it is preferable that it is 0.1 to 3 weight%.

The amount of the imidization catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivatives.

Although the addition amount of another additive changes with the use, it is usually 0-30 weight% of the total weight of a polyamic acid or its derivative, and it is preferable that it is 0.1-10 weight%.

The especially preferable aspect of the liquid crystal aligning agent which can be used by this invention is a composition containing 2 or more types of polyamic acids.

For example, in the case of a liquid crystal aligning agent containing two kinds of polyamic acids, both the first polyamic acid and the tetracarboxylic dianhydride and the diamine using a compound having a side chain structure in one or both of tetracarboxylic dianhydride and diamine The liquid crystal aligning agent containing the 2nd polyamic acid which did not use the compound which has a side chain structure is mentioned. More specifically, one kind of the polyamic acid is a polyamic acid or a derivative I thereof (hereinafter referred to as "polyamic acid I") obtained by reacting one or both of the A component and the B component of an acid with the A component of an amine. And another one is a polyamic acid or derivative II thereof (hereinafter referred to as "polyamic acid II") obtained by reacting one or both of the A component and the B component of the acid with the B component of the amine.

The composition of polyamic acid I and polyamic acid II in this invention is prepared by mixing the above-mentioned polyamic acid I and polyamic acid II. It is preferable that it is I / II = 99/1-50/50, and, as for the weight ratio of the polyamic acid I mixed and polyamic acid II, it is more preferable that I / II = 95/5-80/20. The weight ratio may be appropriately adjusted in accordance with the required pretilt angle, and the pretilt angle can be increased by increasing the ratio of polyamic acid II.

In addition, the liquid crystal aligning agent of this invention may contain only polyamic acid I and II, and may also contain polyamic acid other than polyamic acid I and II, or its derivative (s) further.

Although the diamine I-2 uses 1 type, or 2 or more types of diamines, the diamine represented by the said general formula (II)-(VIII) is used at least. The polyamic acid I synthesized from the A component of the amine and tetracarboxylic dianhydride is also effective in imparting a good ion density to a liquid crystal display device comprising a liquid crystal alignment film formed by using a liquid crystal aligning agent containing the same. .

In addition, diamine I-2 may use arbitrary other diamine together as needed. Here, as other diamine, the diamine represented by the said general formula (VIII)-(XII) and (XV), fluorene type diamine, siloxane type diamine, etc. are mentioned.

The molar ratio of the A component of the amine in the diamine in the polyamic acid I may be adjusted according to the structure of the diamine represented by the general formulas (I) to (VII) selected, desired ion density and long-term reliability, It is preferable that it is 1 to 100%, and it is more preferable that it is 5 to 80%.

On the other hand, the said polyamic acid II is effective also in providing a suitable pretilt angle to the liquid crystal display element containing the liquid crystal aligning film formed using the liquid crystal aligning agent containing this.

Although the 1 type or 2 or more types of diamine represented typically by General formula (VIII)-(XII) can be used for B component of the said amine in the said diamine in the said polyamic acid II, As said diamine which may be used together, the said And diamines, fluorene diamines, and siloxane diamines represented by the general formulas (I) to (VII).

By combining (mixing) said polyamic acid I and polyamic acid II, the characteristic preferable as a liquid crystal aligning agent of this invention can be provided.

Specifically, by appropriately selecting the kind of diamine used and its combination with respect to the diamine which is a raw material of a polyamic acid, a more favorable ion density and an appropriate pretilt angle are provided to the liquid crystal aligning film formed using the composition of this invention. can do.

<5. Liquid crystal aligning film of this invention>

The liquid crystal aligning film of this invention is a liquid crystal aligning film formed by baking the said polyamic acid and the improvement agent in the liquid crystal aligning agent of this invention mentioned above in the film form with respect to the liquid crystal aligning agent of this invention.

The said liquid crystal aligning film apply | coats the liquid crystal aligning agent of this invention to the board | substrate for liquid crystal display elements, or the measurement board | substrates, such as calcium fluoride and silicon, for example, 150-400 degreeC, for example, the film of this liquid crystal aligning agent is preferable. Preferably, it can form by heating to 180-280 degreeC. Here, it is preferable that it is 10-300 nm, and, as for the film thickness of a liquid crystal aligning film, it is more preferable that it is 30-100 nm. Moreover, it is preferable that the liquid crystal aligning film is rubbing process.

The film thickness of the said liquid crystal aligning film can be adjusted with the viscosity of a liquid crystal aligning agent, and the coating method of a liquid crystal aligning agent. In addition, the film thickness of a liquid crystal aligning film can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer. In addition, the component in a liquid crystal aligning film can process hydrolysis etc. as needed, and can analyze using normal analysis means, such as IR and MS.

<6. Liquid crystal display device of the present invention>

The liquid crystal display device of the present invention comprises: 1) a pair of substrates arranged oppositely; 2) a liquid crystal alignment film of the present invention formed on opposing surfaces of each of the pair of substrates; and 3) sandwiched between the pair of substrates. It includes a liquid crystal layer.

It is preferable that the pair of substrates with electrodes arranged opposite to each other be a transparent substrate (for example, a glass substrate).

Electrodes are formed on the surfaces of at least one or both substrates of the pair of substrates corresponding to the shape of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. As such an electrode, ITO, a vapor deposition film of a metal, etc. are mentioned, for example. The electrode may be formed entirely on the surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. The liquid crystal aligning film of this invention is formed on the surface of a board | substrate in the board | substrate with which an electrode is not formed, and an electrode is formed and the liquid crystal aligning film of this invention is formed on an electrode in a board | substrate. Formation of the liquid crystal aligning film of this invention is as above-mentioned.

The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Herein, the liquid crystal composition is not particularly limited, and either of the liquid crystal composition having a positive dielectric anisotropy and the liquid crystal composition having a negative dielectric anisotropy can be used depending on the driving mode.

Examples of preferred liquid crystal compositions having positive dielectric anisotropy include Patent Nos. 3086228, 2,435,435, 5,501, JP-A 8-157826, JP-A 8-231960, and JP. Japanese Patent Application Laid-Open No. 9-241644 (EP885272Al), Japanese Patent Application Laid-Open No. 9-302346, EP806466A1 Japanese Patent Application Laid-Open No. 9-235552, Japanese Patent Application Laid-Open No. 9-235552 9-241643 (EP885271Al), JP 10-204016 (EP844229Al), JP 10-204436, JP 10-231482, JP 2000-087040, JP 2001-48822, etc. have.

The liquid crystal composition which can be used for a VA type liquid crystal display element can be set as the various liquid crystal composition whose negative dielectric constant anisotropy is negative. Examples of preferred liquid crystal compositions include Japanese Patent Application Laid-Open No. 57-114532, Japanese Patent Laid-Open Nos. 2-4725, Japanese Patent Laid-Open Nos. 4-224885, Japanese Patent Laid-Open Nos. 8-40953, Japanese Patent Laid-Open Nos. -168076, JP 10-168453, JP 10-236989, JP 10-236990, JP 10-236992, JP 10-236993, JP 10-236994 JP-A 10-237000, JP 10-237004, JP 10-237024, JP 10-237035, JP 10-237075, JP 10-237076 Japanese Patent Application Laid-Open No. 10-237448 (EP967261Al), Japanese Patent Application Laid-Open No. 10-287874, Japanese Patent Application Laid-Open No. 10-287875, Japanese Patent Application Laid-Open No. 10-291945, Japanese Patent Application Laid-Open No. 11-029581, Japanese Patent Application Laid-Open No. 11-080049 Japanese Patent Application Laid-Open No. 2000-256307, Japanese Patent Application No. 2001-019965, Japanese Patent Application No. 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657, and the like.

The liquid crystal composition having positive or negative dielectric anisotropy can be used by adding one or more optically active compounds.

Of course, the liquid crystal display element of this invention may have another member.

For example, in a TFT type liquid crystal device of color display using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like are formed on the first transparent substrate, and the pixel region is formed on the second transparent substrate. It may have a black matrix, a color filter, a planarization film, a pixel electrode and the like that block other light.

Moreover, in VA type liquid crystal display element, especially MVA type liquid crystal display element, the fine protrusion called domain is formed on the 1st transparent substrate. In addition, spacers may be formed to adjust the cell gap between the substrates.

Although the liquid crystal display device of the present invention can be manufactured by any method, for example, l) a step of applying a liquid crystal aligning agent on the two transparent substrates, 2) a step of drying the applied liquid crystal aligning agent, 3 ) The process of heat-processing necessary for dehydration and ring-closure reaction of the dried liquid crystal aligning agent, 4) The process of orientation-processing the obtained alignment film, 5) Laminating | stacking two board | substrates in the state which has a predetermined clearance gap, It manufactures by the method including the process of putting a liquid crystal in a space | gap, and sealing, or the process of laminating | stacking a liquid crystal on one board | substrate, and then stacking with another board | substrate.

As a coating method in the process of apply | coating the said liquid crystal aligning agent, the spinner method, the printing method, the dipping method, the dropping method, the inkjet method, etc. are generally known. These methods are also applicable to this invention.

Moreover, as a method of the heat processing required for the said drying process and dehydration reaction, the method of heat processing in oven or an infrared furnace, the method of heat processing on a hotplate, etc. are generally known. These methods are also applicable to this invention. It is preferable to perform a drying process at comparatively low temperature (50-140 degreeC) in the range which can evaporate a solvent. It is preferable to perform a heat processing process at the temperature of about 150-300 degreeC generally.

Orientation processing to a liquid crystal aligning film normally carries out a rubbing process in an IPS type liquid crystal display element, an OCB type liquid crystal display element, a TN type liquid crystal display element, and an STN type liquid crystal display element. Although a rubbing process is not performed in many VA type liquid crystal display elements, you may process it.

Next, an adhesive is applied and laminated on one substrate, and the liquid crystal is injected in a vacuum. In the dropping injection method, the liquid crystals are dropped on a substrate before lamination with each other, and then laminated on the other substrate. The adhesive used for lamination is cured by heat or ultraviolet rays to manufacture the liquid crystal display element of the present invention.

In the liquid crystal display element of this invention, a polarizing plate (polarizing film), a wave plate, a light scattering film, a drive circuit, etc. may be mounted.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, the names of the tetracarboxylic dianhydride, diamine, an alkenyl substituted nadiimide compound, a heterocyclic compound, and a solvent which are used for an Example are represented by the following symbols.

[Tetracarboxylic acid dianhydride]

Pyromellitic dianhydride {Structure Formula (1)}: PMDA

1,2,3,4-cyclobutanetetracarboxylic acid dianhydride {Structure Formula (19)}: CBDA

[Diamine]

4,4'-diaminodiphenylmethane {Structure Formula (V-1)}: DDM

4,4 '-[1,3-propanebis (4,1-phenylenemethylene)] bis [benzeneamine] {structural formula (VII-2)}: BABZP3

2- (phenylmethyl) -1,4-diaminobenzene {Structural Formula (IV-16)}: PhPDA

5-[[4- (4'-pentyl [1,1'-bicyclohexyl] -4-yl) phenyl] methyl] -1,3-diaminobenzene {General Formula (VIII-5) / R ²³ = C ₅ H _l1 }: 5ChCh

1,1-bis [4- (4-aminobenzyl) phenyl] -4-heptylcyclohexane {Formula (XI-2) / R ²⁹ = C ₇ H ₁₅ }: 7ChBZ

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (trans-4-npentylcyclohexyl) cyclohexane {General Formula (XI-4) / R ³⁰ = C ₅ H ₁ }: 5ChChBA

4,4'-ethylenedianiline {Structure Formula (V-7)}: DET

[Alkenyl Substituted Nadiimide Compound]

A compound represented by the following structural formula (Ina-1): BANI-M

[Oxylan Compound]

4,4'-methylenebis (N, N-diglycidylaniline): DGA

(3-glycidoxyoxy) trimethoxysilane: TMS

(3-glycidoxyoxy) methyldimethoxysilane: DMS

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane: ECS

Oxetane Compound

Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene: BMMB

[Aziridine Compound]

2,4,6-tris (1'-aziridinyl) -1,3,5-triazine: ATA

[Tyran compound]

N, N, N ', N'-tetrakistyranylmethyl-4,4'-diaminodiphenylmethane: TMAP

[Oxazoline Compound]

Poly (styrene-co-2-isopropenyl-oxazoline) (Product: Epocross RPS-1005): PSO

[Oxadine Compound]

Bis (3-phenyl-3,4-dihydro-2H-1,3-benzooxadin-6-yl) methane (benzoxadine F-a type from Bukko Chemical Co., Ltd.): BOZ

[catalyst]

N-methyl-2-pyrrolidone: NMP

Butyl cellosolve (ethylene glycol monobutyl ether): BC

<1. Synthesis of Polyamic Acid>

[Synthesis of Polyamic Acid]

Synthesis Example  One

In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 1.6760 g of 5ChCh, 1.7918 g of PhPDA, and 58.3 g of dehydrated NMP were added and stirred and dissolved under a dry nitrogen stream. Next, 2.5321 g of CBDA was added and reacted for 30 hours in a room temperature environment. When reaction temperature rises during reaction, reaction temperature was suppressed to about 70 degreeC or less and made to react. To the obtained solution, 37.7 g of BC was added to synthesize a polyamic acid solution (PAl) having a concentration of 6% by weight. The weight average molecular weight of obtained PA1 was 37,000.

Here, the weight average molecular weight of a polyamic acid dilutes the obtained polyamic acid with the dilution liquid (phosphoric acid / DMF = 0.6 / 100: weight ratio) which consists of phosphoric acid and DMF so that a polyamic acid concentration may be about 1 weight%, and is chromatographic. Using the pack C-R7A (manufactured by Shimadus Corporation), the dilution liquid was measured by GPC method as a developing agent and determined by polystyrene conversion. On the other hand, the column was measured under conditions of a column temperature of 50 ° C. and a flow rate of 0.6 mL / min using GF-7HQ (manufactured by Wawa Denki Kogyo Co., Ltd.).

Synthesis Example  2 to 6

As shown in Table 1, the polyamic acid solutions (PA2-PA6) were synthesize | combined according to the synthesis example 1 except having changed the tetracarboxylic dianhydride and diamine. The results are summarized in Table 1, including Synthesis Example 1.

TABLE 1

<2. Manufacturing of Liquid Crystal Display Devices>

Example 1

The 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and the 6% by weight polyamic acid solution (PA2) synthesized in Synthesis Example 2 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, and DGA, which is an oxirane compound, were added per 100 parts by weight of the polyamic acid, respectively, so that the total amount of the modifier composed of these compounds was 20 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured as follows.

Manufacturing method of liquid crystal display element

The liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with the spinner, and the film | membrane of 70 nm of film thickness was formed. After coating and heating at 80 degreeC for about 5 minutes, it heat-processed at 220 degreeC for 40 minutes, and then carrying out a rubbing process, and formed the liquid crystal aligning film.

The liquid crystal aligning film formed on the glass substrate was ultrasonically cleaned for 5 minutes in ultrapure water, and then dried at 120 ° C. for 30 minutes in an oven.

After spread | dispersing a 4 micrometers gap material on one glass substrate, the surface in which the liquid crystal aligning film was formed was made inside, and a rubbing direction was made in parallel, and a pair of glass substrates in which the liquid crystal aligning film was formed opposed was arranged, The perimeter was sealed with an epoxy curing agent to prepare an antiparallel cell with a gap of 4 μm. The following liquid crystal composition I was injected into the said gap, and the injection hole for liquid crystal compositions was sealed with the photocuring agent. Subsequently, it heat-processed at 110 degreeC for 30 minutes, and manufactured the liquid crystal display element.

Liquid Crystal Composition I

Example 2

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, and BOZ, which is an oxadine compound, were added per 100 parts by weight of each polyamic acid, and the total amount of the modifiers composed of these compounds was 20 parts by weight. . Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 3

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, and BMMB, which is an oxetane compound, were added per 100 parts by weight of the polyamic acid, respectively, so that the total amount of the modifier composed of these compounds was 20 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 4

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl substituted nadiimide compound, and ATA, which is an aziridine compound, were added per 100 parts by weight of the polyamic acid, respectively, so that the total amount of the modifiers composed of these compounds was 20 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 5

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl substituted nadiimide compound, and TMAP, which is a thiirane compound, were added per 100 parts by weight of the polyamic acid, respectively, to make 20 parts by weight of the total amount of the improver composed of these compounds. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 6

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, and PSO, which is an oxazoline compound, were added per 100 parts by weight of the polyamic acid, respectively, and the total amount of the modifiers composed of these compounds was 20 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 7

A 5% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 30 parts by weight of BANI-M, which is an alkenyl substituted nadiimide compound, is added per 100 parts by weight of the polyamic acid, and 10 parts by weight of BOZ, which is an oxadine compound, is added per 100 parts by weight of the polyamic acid to form the compound The total amount of the modifier was 40 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Comparative Example 1

The 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and the 6% by weight polyamic acid solution (PA2) synthesized in Synthesis Example 2 were mixed at a weight ratio of 1/9. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Comparative Example 2

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, the polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Comparative Example 3

A 6% by weight polyamic acid solution (PAl) synthesized in Synthesis Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of BANI-M, which is an alkenyl substituted nadiimide compound, was added per 100 parts by weight of the polyamic acid. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

[Comparative Example 4]

The 6% by weight polyamic acid solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10 parts by weight of PS0, which is an oxazoline, was added per 100 parts by weight of the polyamic acid. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 8

To the polyamic acid solution (PA3) having a concentration of 6% by weight synthesized in Synthesis Example 3, 10 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, and DGA, which is an oxirane compound, were added per 100 parts by weight of the polyamic acid, respectively, The total amount of the improving agent which consists of compounds was 20 weight part. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1 except having used liquid crystal composition II shown below.

Liquid Crystal Composition II

Example 9

To the polyamic acid solution (PA2) having a concentration of 6% by weight synthesized in Synthesis Example 2, 10 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, and BOZ, which is an oxadine compound, were added per 100 parts by weight of the polyamic acid, respectively. The total amount of the improving agent consisting of these compounds was 20 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1 except having used liquid crystal composition II.

[Comparative Example 5]

To the polyamic acid solution (PA3) having a concentration of 6% by weight synthesized in Synthesis Example 3, 20 parts by weight of BANI-M, which is an alkenyl substituted nadiimide compound, was added per 100 parts by weight of the polyamic acid. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1 except having used liquid crystal composition II.

Example 10

A 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, is added per 100 parts by weight of the polyamic acid, and 20 parts by weight of TMS, which is an oxirane compound, is added per 100 parts by weight of the polyamic acid, thereby improving the composition comprising these compounds. The total amount of was set to 40 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 11

A 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, is added per 100 parts by weight of the polyamic acid, and 20 parts by weight of DMS, which is an oxirane compound, is added per 100 parts by weight of the polyamic acid, thereby improving the composition comprising these compounds. The total amount of was set to 40 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 12

A 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, is added per 100 parts by weight of the polyamic acid, and 20 parts by weight of ECS, which is an oxirane compound, is added per 100 parts by weight of the polyamic acid, thereby improving the composition comprising these compounds. The total amount of was set to 40 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 13

The 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and the 6% by weight polyamic acid solution (PA6) synthesized in Synthesis Example 6 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, is added per 100 parts by weight of the polyamic acid, and 20 parts by weight of TMS, which is an oxirane compound, is added per 100 parts by weight of the polyamic acid, thereby improving the composition comprising these compounds. The total amount of was set to 40 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Example 14

The 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and the 6% by weight polyamic acid solution (PA6) synthesized in Synthesis Example 6 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, is added per 100 parts by weight of the polyamic acid, and 20 parts by weight of ECS, which is an oxirane compound, is added per 100 parts by weight of the polyamic acid, thereby improving the composition comprising these compounds. The total amount of was set to 40 parts by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Comparative Example 6

A 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-M, which is an alkenyl substituted nadiimide compound, was added per 100 parts by weight of the polyamic acid. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Comparative Example 7

A 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of ECS, which is an oxirane compound, was added per 100 parts by weight of the polyamic acid. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

Comparative Example 8

A 6% by weight polyamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 weight% with respect to the whole, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured by the method similar to Example 1.

<3. Evaluation of Electrical Characteristics>

[Test Examples 1 to 22]

About the liquid crystal display element manufactured in Examples 1-14 and Comparative Examples 1-8, the measurement of ion density and the long-term reliability of an electrical property were performed as follows.

1) Measurement of ion density

The ion density was measured using the liquid crystal physical property evaluation apparatus 6254 type made from Toyang Technica. Measurement conditions were waveform: triangle wave, frequency: 0.0 lHz, voltage: ± 10 V, and measurement temperature was 60 degreeC. The smaller this value, the better the electrical characteristics. The results are shown in Table 2.

2-1) Measurement of Retention Characteristics of Ion Density [Test Examples 1 to 14]

About the manufactured liquid crystal display element, the ion density [pC] over time was calculated | required, and the retention characteristic was evaluated. As the test method of the retention characteristics, the liquid crystal display element was left to stand for 100 hours in a temperature of 60 ° C., and a method of measuring ion density [pC] along the course of time was employed. The smaller the decrease in ion density (e.g., the increase rate is less than 1.5 times: increase rate (times) = ion density after 100 hours / ion density at initial (0 hours)), the retention characteristics of the ion density can be said to be good, In addition, it can be said that the long-term reliability of the electrical characteristics is good. The results are shown in Table 2.

TABLE 2

2-2) Measurement of Retention Characteristics of Ion Density [Test Examples 15 to 22]

About the manufactured liquid crystal display element, ion density [pC] over time was calculated | required, and the retention characteristic was evaluated. In the test method of the holding characteristic, the liquid crystal display element was left to stand for 100 hours in the temperature of 100 degreeC atmosphere, and the method of measuring ion density [pC] with time is employ | adopted. The smaller the decrease in ion density (e.g., the increase rate is less than 5.0 times: increase rate (times) = ion density after 100 hours / initial density (0 hours)), the retention characteristics of the ion density can be said to be good, In addition, it can be said that the long-term reliability of the electrical characteristics is good. The results are shown in Table 3.

TABLE 3

As shown in Table 2 and Table 3, in the case of the liquid crystal display element using the liquid crystal aligning film which mixed the above-mentioned improvement agent, the fall of the retention characteristic of ion density was suppressed remarkably.

As mentioned above, when the liquid crystal aligning agent containing the polyamic acid in this invention and the improving agent of the said base material is a liquid crystal aligning film of a liquid crystal display element, ion density is high and it can suppress remarkably the fall of the holding characteristic at the same time. Can be.

Claims (20)

As a liquid crystal aligning agent containing a polyamic acid or its derivative (s), an alkenyl substituted nadiimide compound, and a heterocyclic compound, The heterocyclic compound has a 1 or 2 or more heterocyclic structure selected from the group consisting of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxadine. The method of claim 1, Said alkenyl substituted nadiimide compound is a compound represented with the following general formula (Ina), The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (Ina), R <^1> and R <^2> represents hydrogen, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, aryl, or benzyl, respectively, and n is An integer of 1 to 2; when n = 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl, _and- (C _q H _2q ) -O. _t- (C _r H _2r O) _u -C _s H _{2s +1} (q, r, s represents an integer from 2 to 6, respectively, t represents 0 or 1, u represents an integer from 1 to 30) Polyoxyalkylene alkyl represented by),-(R) _v -C ₆ H ₄ -R ⁴ (v represents 0 or 1, R represents alkylene having 1 to 4 carbon atoms, R ⁴ is hydrogen or Group represented by alkyl having 1 to 4 carbon atoms, -C ₆ H ₄ -TC ₆ H ₅ (T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -S- or- SO ₂ - group represented by represents a), or 1 to 3 hydrogen directly bonded to the aromatic ring of these groups represents a group that which may be substituted with a hydroxyl group; n = 2 il gyeong , R ³ is a cycloalkylene, alkylene having a carbon number of 5 to 8 carbon atoms of _{2~20 - (C q H 2q O} ) t - (C r H 2r O) u -C s H 2s - (q, r, s represents an integer of 2 to 6, t represents 0 or 1, and u represents an integer of 1 to 30), polyoxyalkylene represented by arylene having 6 to 12 carbon atoms,-(R) _v -C ₆ H ₄ -R _5- (v represents 0 or 1, R and R ⁵ each represent alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms), -C ₆ H ₄ -TC ₆ H _4- (T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ O-, -S-, or -SO _2- , or a group in which 1 to 3 hydrogens directly bonded to the aromatic ring of these groups may be substituted with hydroxyl groups. The method of claim 2, The said alkenyl substituted nadiimide compound contains the compound 1 or 2 or more represented by the following structural formula (Ina-1)-(Ina-3), The liquid crystal aligning agent characterized by the above-mentioned.

The method according to any one of claims 1 to 3, 1-100 weight part of said alkenyl substituted nadiimide compounds are contained in total amount with respect to 100 weight part of said polyamic acids or its derivatives, The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 1 to 4, The said heterocyclic compound contains the compound which has 2 or more of said heterocyclic structures, and contains 1-100 weight part of said compounds in total amount with respect to 100 weight part of said polyamic acids or its derivative (s). The method according to any one of claims 1 to 5, The said polyamic acid or its derivative is polyamic acid obtained by making tetracarboxylic dianhydride and an amine component react as a acid component, and are polyamic acid obtained, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 6, The said acid component contains A component and B component, The A component of an acid contains aromatic tetracarboxylic dianhydride, The said aromatic tetracarboxylic dianhydride has following structural formula (1), (2), (5)-( It is 1 or 2 or more compound chosen from the group which consists of 7) and (14), The liquid crystal aligning agent characterized by the above-mentioned.

The method of claim 7, wherein Said aromatic tetracarboxylic dianhydride is a compound of the said Formula (1), The liquid crystal aligning agent characterized by the above-mentioned. The method according to claim 7 or 8, B component of the said acid contains any one or both of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 9, The aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride are represented by the following structural formulas (19), (23), (25), (35) to (37), (39), (44), and (49). It is 1 or 2 or more compound chosen from the group which consists of liquid crystal aligning agents characterized by the above-mentioned.

The method of claim 10, Said alicyclic tetracarboxylic dianhydride is said structural formula (19), The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 6 to 11, The said amine component contains A component individually or both components of A component and B component, The A component of the said amine is a 1 or 2 or more general formula chosen from the group which consists of following General formula (I)-(VII). It is a compound displayed, The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (I), A ¹ represents-(CH ₂ ) _m-, where m represents an integer of 1 to 12. Also, in general formulas (III), (V) and (VII) , A ¹ independently, a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m -S-, wherein m is independently 1 It represents an integer of to 12 Further, in the general formula (VI), a ² are independently a single bond, -O-, -S-, -CO-, -C (CH 3) 2 -., -C (CF ₃ ) ₂ -or alkylene having 1 to 6. In addition, hydrogen bonded to a cyclohexane ring or a benzene ring of the general formulas (II) to (VII) is independently -F, -CH ₃ ,- May be substituted with OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl.) The method of claim 12, The A component of the amine is represented by the following structural formulas (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12), (V-33) and It is 1 or 2 or more compound chosen from the group which consists of (VII-2), The liquid crystal aligning agent characterized by the above-mentioned.

The method according to claim 12 or 13, The B component of the said amine is a compound represented by 1 or 2 or more general formula chosen from the group which consists of following General formula (VIII)-(XII), The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (VIII), R ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O- or-(CH ₂ ) _e- , e represents an integer of 1 to 6, R ² represents a group having a steroid skeleton, a group represented by the following general formula (XIII), alkyl having 1 to 30 carbon atoms, or phenyl; If the ethylene and the alkyl have 2 or more carbon atoms, any of -CH ₂ -can be independently substituted with -O-, -CH = CH- or -C≡C-, provided that oxygen is not continuous ), Hydrogen of the phenyl may be independently substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy, except when -R ¹ -R ² represents benzyl box. In addition, in formula (IX), R ³ independently represents hydrogen or methyl; R ⁴ represents hydrogen or alkyl having 1 to 30 carbon atoms; R ⁵ independently represents a single bond, -CO- or -CH _2- . In addition, in formula (X), R ³ independently represents hydrogen or methyl; R ⁴ represents hydrogen or alkyl having 1 to 30 carbon atoms; R ⁵ independently represents a single bond, -CO- or -CH _2- ; R ⁶ and R ⁷ each independently represent hydrogen, alkyl having 1 to 30 carbon atoms, or phenyl. In formula (XI), R ⁸ represents hydrogen or alkyl having 1 to 30 carbon atoms, and any —CH ₂ — of the above alkyl having 2 or more carbon atoms is independently —O—, —CH═CH— or — C≡C-, provided that oxygen is not continuous; R ⁹ independently represents —O— or alkylene having 1 to 6 carbon atoms; Ring A represents 1,4-phenylene or 1,4-cyclohexylene; a represents 0 or 1; b represents 0, 1 or 2; c represents 0 or 1 independently. In general formula (XII), R ¹⁰ represents alkyl having 3 to 30 carbons or fluorinated alkyl having 3 to 30 carbons; R ¹¹ represents hydrogen, alkyl of 1 to 30 carbon atoms, or fluorinated alkyl of 1 to 30 carbon atoms; R ¹² independently represents —O— or alkylene having 1 to 6 carbon atoms; d independently represents O or 1)

(In general formula (XIII), R ^l3 , R ¹⁴ And R ¹⁵ are each independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms, provided that oxygen is not continuous ) Or alkyleneoxy having 1 to 3 carbon atoms, provided that oxygen is not continuous; R ¹⁶ and R ¹⁷ each independently represent hydrogen, fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkoxyalkyl having 2 to 30 carbon atoms, fluoromethyl, difluoromethyl, trifluoromethyl, fluorome Methoxy, difluoromethoxy or trifluoromethoxy, and any —CH ₂ — in the alkyl, alkoxy and alkoxyalkyl having 2 or more carbon atoms is a group represented by difluoromethylene or the following general formula (XIV) May be substituted; Ring B and ring C each independently represent 1,4-phenylene or 1,4-cyclohexylene; f, g and h each independently represent an integer of 0 to 4; i, j and k each independently represent an integer of 0 to 3, and the sum thereof is 1 or more; 1 and m each independently represent 1 or 2)

(In General Formula (XIV), R ¹⁹ , R ²⁰ , R ^21, and R ²² each independently represent alkyl having 1 to 10 carbon atoms, or phenyl, and n represents an integer of 1 to 100.) The method of claim 14, The B component of the amine is selected from the group consisting of the following general formulas (VIII-2), (VIII-4), (VIII-5), (VIII-6), (XI-2) and (XI-4). It is a compound represented by the general formula of 1 or 2 or more, The liquid crystal aligning agent characterized by the above-mentioned.

(In the general formula, R ²³ independently represents alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or alkyl having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or 1 to 20 carbon atoms. Represents alkyl of) The method according to any one of claims 1 to 15, Two or more types of said polyamic acid or its derivatives are contained, The liquid crystal aligning agent characterized by the above-mentioned. As a liquid crystal aligning agent containing a polyamic acid or its derivative (s), an alkenyl substituted nadiimide compound, and a heterocyclic compound, Said polyamic acid or its derivative is a polyamic acid obtained by making tetracarboxylic dianhydride as an acid component and diamine as an amine component, The acid component includes an A component and a B component, and the A component of the acid is one or two or more selected from the group consisting of the following structural formulas (1), (2), (5) to (7) and (14) Compound, wherein the B component of the acid is selected from the group consisting of the following structural formulas (19), (23), (25), (35) to (37), (39), (44), and (49). Or two or more compounds, The amine component includes component A alone or both components of component A and component B, and the component A of the amine includes the following structural formulas (IV-1), (IV-2), (IV-15), and (IV-16) ), (V-1) to (V-12), (V-33) and (VII-2), one or two or more compounds selected from the group consisting of the amines of the amines of the following general formula (VIII- 2), (VIII-4), (VIII-5), (VIII-6), (XI-2) and (XI-4), a compound represented by one or two or more general formulas selected from the group consisting of The alkenyl substituted nadiimide compound includes one or two or more of the compounds represented by the following structural formulas (Ina-1) to (Ina-3), The said heterocyclic compound is a liquid crystal aligning agent which has 1 or 2 or more heterocyclic structures chosen from the group which consists of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxadine.

(In the above general formula, R ²³ independently represents alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or alkyl having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or 1 to 20 carbon atoms. Represents alkyl of)

The method of claim 17, A component of the acid is a compound represented by the structural formula (1), B component of the acid is a compound represented by the structural formula (19), The component A of the amine is one or two or more compounds represented by the structural formulas (IV-16), (V-1), (V-7) and (VII-2), and the B component of the amine is the general formula 1 or 2 or more compounds represented by (VIII-5), (XI-2) and (XI-4), The alkenyl substituted nadiimide compound is a compound represented by the structural formula (Ina-1), The heterocyclic compound may be 4,4'-methylenebis (N, N-diglycidylaniline), (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 2,4,6-tris (1'-aziridinyl ) -1,3,5-triazine, N, N, N ', N'-tetrakistyranylmethyl-4,4'-diaminodiphenylmethane, poly (styrene-co-2-isopropenyl -Oxazoline), and bis (3-phenyl-3,4-dihydro-2H-1,3-benzooxadin-6-yl) methane, characterized in that it comprises one or more compounds selected from the group consisting of Liquid crystal aligning agent to be. The liquid crystal aligning film in any one of Claims 1-18 is formed by baking in the state of a film | membrane, The liquid crystal aligning film characterized by the above-mentioned. A pair of substrates arranged oppositely, electrodes formed on one or both sides of the opposing surfaces of each of the pair of substrates, liquid crystal alignment films formed on the opposing surfaces of the pair of substrates, and the pair of In the liquid crystal display element which has a liquid crystal layer formed between board | substrates, The said liquid crystal aligning film is a liquid crystal aligning film of Claim 19, The liquid crystal display element characterized by the above-mentioned.