TWI427121B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal display element comprising the liquid crystal alignment film, wherein the liquid crystal alignment agent is selected from the group consisting of polylysine and the polyamic acid. At least one polymer of the derivative, substituted with an alkenyl group, nadimide (ie, endo-5-norbornene-2,3-dimethylimine (Endo-5-norbornene) -2,3-dicarboximide)) A modifier in which at least one of a compound and a heterocyclic compound having a specific heterocyclic structure are combined is dissolved in a solvent to form a solution.

The liquid crystal display device is currently used in various liquid crystal display devices such as a viewfinder of a notebook computer and a desktop computer, a viewfinder of a camera, and a projection display, and has recently been applied to televisions. Furthermore, it is also used for optoelectronics-related components such as optical printer heads, optical Fourier transform elements, and light valves.

The liquid crystal display device generally has: (1) an opposite electrode disposed on the substrate, (2) an electrode formed on one surface or both surfaces of the pair of substrates, and (3) an opposite surface of each of the pair of substrates a liquid crystal alignment film formed thereon and (4) a liquid crystal layer formed between the pair of substrates.

As a conventional liquid crystal display element, a mainstream display device using a nematic liquid crystal is currently performing (1) a TN (Twisted Nematic) type liquid crystal display element which is twisted at 90 degrees ( 2) STN (Super Twisted Nematic) type liquid crystal display element which is usually twisted at 180 degrees or more, and (3) Practical use of a so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor Chemical. These liquid crystal display elements can appropriately see that the angle of view of the image is narrow, and have the following disadvantages: deterioration in brightness and contrast when viewed from an oblique direction and generation of brightness inversion in halftone.

In recent years, (1) TN-TFT type liquid crystal display elements using optical compensation films, (2) VA (Vertical Alignment) type liquid crystal display elements using vertical alignment and optical compensation films, (3) will be vertical MVA (Multi Domain Vertical Alignment) type liquid crystal display element used in combination with the protrusion structure technology, or (4) IPS (In-Plane Switching) type liquid crystal display element of a lateral electric field effect type, (5) ECB (Electrically Controlled Birefringence) type liquid crystal display element, (6) Optically Compensated Bend or Optically self-Compensated Birefringence (OCB) type liquid crystal display element Other technologies improve the problem of the viewing angle, and the improved technology is put into practical use or research.

The technical development of the liquid crystal display device is not only improved by these driving methods and device structures, but also by improvement of the constituent members used for the liquid crystal display device. Among the constituent members used for the liquid crystal display element, in particular, the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element, and the role of the liquid crystal display element in improving the quality of the liquid crystal alignment film becomes more and more important. .

The liquid crystal alignment film is prepared from a liquid crystal alignment agent. At present, the so-called liquid crystal alignment agent mainly used refers to a solution in which polylysine or soluble polyimine is dissolved in an organic solvent. The solution is formed by coating such a solution on a substrate, followed by heating, etc., to form a polyimide film. Various liquid crystal alignment agents other than polyglycolic acid have been studied, but heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical properties, optical properties, display properties, and the like have been studied. In terms of terms, it has hardly been put into practical use.

As an important characteristic required for a liquid crystal alignment film for improving the display quality of a liquid crystal display element, an ion density is mentioned. If the ion density is low, the voltage applied to the liquid crystal during the frame period is lowered, resulting in a decrease in luminance and an influence on the normal harmonic display. Further, there is a problem that, for example, even if the initial ion density is high, the ion density (long-term reliability) after the high-temperature accelerated test is also lowered.

As an attempt to solve the aforementioned problems, the industry has recently proposed several methods.

(1) A polyglycine composition in which two or more polyamic acids having different physical properties for forming a liquid crystal alignment film are combined is known (for example, refer to Patent Documents 1 and 2).

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

(3) A varnish composition containing two or more polyamic acids and polyamines having different physical properties and a solvent is known (for example, refer to Patent Document 4).

(4) A varnish composition containing a polymer material containing a polyamine acid synthesized using a diamine compound having a specific structure (for example, see Patent Document 5).

(5) A technique of adding a low molecular weight epoxy resin to a polyimide and a polyimide varnish (for example, see Patent Document 6).

Further, the company has proposed several techniques for solving the following problems: This problem includes improving the performance of a liquid crystal display element by adding an additive to polyamic acid. As such a technique, for example, a liquid crystal alignment agent containing a polyamic acid and a hardening accelerator having an oxazine structure or an oxazine structure (for example, refer to Patent Document 7), and contains a polyfluorene. A liquid crystal alignment agent in which an amino acid and an alkenyl group are substituted with a nadic acid ylide compound (for example, refer to Patent Documents 8 and 9), and a liquid crystal alignment agent containing a polyamic acid and an epoxy group-containing compound (for example, refer to Patent Document 10 and 11).

Further, the company has proposed a number of techniques for solving the problem of improving the performance of a liquid crystal display element by adding an additive to a compound for photoalignment. As such a technique, for example, a composition for photo-alignment containing a dichroic molecule and a compound having a dimercaptoamine group as a radical polymerizable group (for example, see Patent Document 12).

However, with these prior art techniques, the problems of ion density and long-term reliability cannot be adequately solved. For example, Patent Document 7 discloses evaporation, sublimation, and decomposition in the imidization of a liquid crystal alignment film, and electrical characteristics of a curing accelerator to a liquid crystal alignment film in a liquid crystal alignment film produced by using such a liquid crystal alignment film. The impact was not studied.

Further, for example, in Patent Document 11, the problem also includes adsorption of ionic impurities, and in the examples, the voltage holding ratio of the liquid crystal display element is described. However, although the voltage holding ratio is also related to the ion density, the initial voltage holding ratio is not related to the diachronic ion density. The reason for this is considered to be that the ionic impurities are included in the element not only when the liquid crystal display element is produced, but also because of the ionic impurities generated by the decomposition of the liquid crystal accompanying the operation of the liquid crystal display element, and which change over time. Therefore, it is generally considered that the technique of Patent Document 11 for adsorbing ionic impurities can effectively reduce the ionic impurities contained in the elements when the liquid crystal display element is produced, but further research is needed to suppress the occurrence of ionic impurities. .

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-193347 (Patent Document 2) Japanese Patent Laid-Open No. Hei 11-193347 (Patent Document 3) International Publication No. 00/61684 (Patent Document 4) International Publication 01/000733 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 12] Japanese Patent Laid-Open Publication No. 2003-270638

In view of the above circumstances, it is desired to develop a liquid crystal alignment agent for a liquid crystal display element which improves the long-term reliability problem of electrical characteristics accompanying changes in ion density and ion density, and a liquid crystal alignment film formed using the liquid crystal alignment agent. And a liquid crystal display element including the liquid crystal alignment film.

The present inventors have made diligent research to solve the above problems. As a result, it has been found that a good liquid density and long-term reliability can be imparted to a liquid crystal display element having a liquid crystal alignment film which is selected from a derivative selected from the group consisting of polylysine and the poly-proline. At least one polymer further comprising an alkenyl-substituted nadic acid ruthenium imide compound selected from the group consisting of having oxirane, oxetane, thiirane, aziridine ( The present invention has been completed by preparing a liquid crystal alignment agent of a modifier obtained by combining at least one of aziridine, an oxazoline and a compound having an oxazine structure.

Further, it has been found that a liquid crystal alignment film produced by appropriately selecting the polyamic acid and using the liquid crystal alignment agent can be suitably applied to liquid crystal display elements of various display driving methods.

The present invention encompasses the following constitution.

[1] A liquid crystal alignment agent which is a liquid crystal alignment agent comprising polylysine or a derivative thereof, an alkenyl-substituted nadic acid ruthenium imine compound, and a heterocyclic compound, characterized in that the heterocyclic compound has One or more selected from the group consisting of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxazine Heterocyclic structure.

[2] The liquid crystal alignment agent according to [1], wherein the alkenyl-substituted nadic acid ylide compound is a compound represented by the following formula (Ina).

[Chemical 1]

In the formula (I na), R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or benzyl group. And n represents an integer of 1 to 2; and when n=1, R ³ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a benzyl group. -(C _q H _2q )-O _t -(C _r H _2r 0) _u -C _s H _2s+1 (q, r, s represent integers from 2 to 6, respectively, t represents 0 or 1, u represents 1~ a polyoxyalkylene alkyl group represented by an integer of 30, with -(R) _v -C ₆ H ₄ -R ⁴ (v represents 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, R ⁴ a group represented by hydrogen or an alkyl group having 1 to 4 carbon atoms, and -C ₆ H ₄ -T-C ₆ H ₅ (T represents -CH ₂ -, -C(CH ₃ ) ₂ , -CO-, a group represented by -S- or -SO ₂ -), or a group in which 1 to 3 hydrogens directly bonded to the aromatic ring are substituted with a hydroxyl group; when n=2, R ³ represents a carbon number of 2 to 20 The alkylene group, cycloalkylene having a carbon number of 5-8, and -(C _q H _2q O) _t -(C _r H _2r O) _u -C _s H _2s -(q, r, s Representing an integer of 2 to 6, respectively, t is 0 or 1, and u is an integer represented by 1 to 30. Group, an arylene group having a carbon number (arylene) 6 ~ 12 to _{- (R) v -C 6 H} 4 -R 5 - (v represents 0 or 1, R and R ⁵ each represent a carbon number of 1 to 4 extends a group represented by an alkyl group or a cycloalkyl group having 5 to 8 carbon atoms, and -C ₆ H ₄ -T-C ₆ H ₄ - (T represents -CH ₂ -, -C(CH ₃ ) ₂ -, a group represented by -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ O-, -S-, or -SO ₂ -), or an aromatic ring of these groups Directly bonded 1 to 3 hydrogens are substituted by a hydroxyl group.

[3] The liquid crystal alignment agent according to [2], wherein the alkenyl-substituted nadic acid ruthenium imide compound is represented by the following structural formula (I na-1) to (I na-3) One or more of the compounds.

[4] The liquid crystal alignment agent according to [1] to [3], which is characterized in that it is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polyaminic acid or its derivative (in total) The alkenyl group replaces the nadic acid ylide imide compound.

[5] The liquid crystal alignment agent according to [1] to [4], wherein the heterocyclic compound contains a compound having two or more heterocyclic structures, and the liquid crystal alignment agent comprises or is relative to polyamic acid or 100 parts by weight of the derivative is 1 to 100 parts by weight (based on the total amount) of the compound.

[6] The liquid crystal alignment agent according to [1] to [5], wherein the poly-proline or a derivative thereof is a tetracarboxylic dianhydride as an acid component and two as an amine component. Polylysine obtained by amine reaction.

[7] The liquid crystal alignment agent according to [6], wherein the acid component contains the A component and the B component, and the acid component A contains the aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride is One or two or more compounds selected from the group consisting of the following structural formulae (1), (2), (5) to (7), and (14).

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

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

[10] The liquid crystal alignment agent according to [9], wherein the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are selected from the following structural formulas (19) and (23). One or two or more compounds of the group consisting of (25), (35) to (37), (39), (44), and (49).

[11] The liquid crystal alignment agent according to [10], wherein the alicyclic tetracarboxylic dianhydride is a compound of the formula (19).

[12] The liquid crystal alignment agent according to [6] to [11], wherein the amine component contains the component A alone or two components of the component A and the component B, and the component A of the amine is selected from the group consisting of One or two or more compounds represented by the formulae of the general formula (I) to (VII).

[Chemical 5] H ₂ N-A ¹ -NH ₂ (I)

In the formula (I), A ¹ represents -(CH ₂ ) _m . Here, m represents an integer from 1 to 12. Further, in the general formulae (III), (V), and (VII), A ¹ independently represents a single bond, -O-, -S-, -S-S-, -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-. Here m independently represents an integer from 1 to 12. Further, in the formula (VI), A ² independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or a carbon number of 1. ~6 alkylene. Further, hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulae (II) to (VII) may be independently substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H , -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl.

[13] The liquid crystal alignment agent according to [12], wherein the A component of the amine is selected from the following structural formulae (IV-1), (IV-2), (IV-15), ( One or more compounds of the group consisting of IV-16), (V-1)~(V-12), (V-33) and (VII-2).

[14] The liquid crystal alignment agent according to [12] or [13] wherein the component B of the amine is one selected from the group consisting of the following general formulae (VIII) to (XII) or Two or more compounds represented by the general formula.

[Chemistry 7]

In the formula (VIII), R ¹ represents 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 formula (XIII), an alkyl group having 1 to 30 carbon atoms, or a phenyl group; And when the carbon number of the alkyl group is 2 or more, any -CH ₂ - thereof may be independently substituted by -O-, -CH=CH- or -C≡C- (wherein the oxygen is discontinuous), hydrogen of the phenyl group It may also be independently substituted by fluorine, methyl, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy, except that -R ¹ -R ² represents a benzyl group.

Further, in the formula (IX), R ³ independently represents hydrogen or a methyl group; R ⁴ represents hydrogen or an alkyl group having 1 to 30 carbon atoms; and R ⁵ independently represents a single bond, -CO- or -CH ₂ -.

Further, in the formula (X), R ³ independently represents hydrogen or a methyl group; R ⁴ represents hydrogen or an alkyl group having 1 to 30 carbon atoms; and R ⁵ independently represents a single bond, -CO- or -CH ₂ -; R ⁶ and R ⁷ each independently represent hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group.

Further, in the formula (XI), R ⁸ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group having 2 or more carbon atoms may be independently -O-, -CH=CH- Or -C≡C-substitution (wherein the oxygen is discontinuous); R ⁹ independently represents -O- or an alkylene group having 1 to 6 carbon atoms; and ring A represents a 1,4-phenylene group or a 1,4-cyclode. Hexyl; a represents 0 or 1; b represents 0, 1 or 2; c independently represents 0 or 1.

Further, in the formula (XII), R ¹⁰ represents an alkyl group having 3 to 30 carbon atoms or a monofluoroalkyl group having 3 to 30 carbon atoms; and R ¹¹ represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or carbon. a monofluorinated alkyl group of 1 to 30; R ¹² independently represents -O- or an alkylene group having 1 to 6 carbon atoms; and d independently represents 0 or 1.

In the formula ( ^XIII ), R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and carbon. Number 1 to 3 of an oxygen alkyl group (wherein oxygen is discontinuous), or a carbon number of 1 to 3 alkyleneoxy group (wherein oxygen is discontinuous); and R ¹⁶ and R ¹⁷ independently represent hydrogen, fluorine or A R ¹⁸ represents hydrogen, fluorine, chlorine, cyano, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a monofluoromethyl group. Difluoromethyl, trifluoromethyl, monofluoromethoxy, difluoromethoxy or trifluoromethoxy; any -CH of alkyl, alkoxy and alkoxyalkyl groups having 2 or more carbon atoms ₂ - may be substituted by a difluoromethylene group or a group represented by the following formula (X IV); ring B and ring C each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group; , g and h respectively represent an integer of 0 to 4, respectively; i, j, and k each independently represent an integer of 0 to 3, and the total of these values is 1 or more; and l and m each independently represent 1 or 2.

In the formula (X IV), R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 1 to 100.

[15] The liquid crystal alignment agent according to [14], wherein the component B of the amine is selected from the group consisting of the following general formulae (VIII-2), (VIII-4), (VIII-5), A compound represented by one or two or more formulas of the group consisting of (VIII-6), (XI-2) and (XI-4).

In the formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or a carbon number of 1. ~20 alkyl.

[16] The liquid crystal alignment agent according to [1] to [15], which comprises two or more kinds of polyaminic acid or a derivative thereof.

[17] A liquid crystal alignment agent, which is a liquid crystal alignment agent comprising polylysine or a derivative thereof, an alkenyl-substituted nadic acid ruthenium imine compound, and a heterocyclic compound, wherein the polylysine or its derivative The polyamino acid obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component, the acid component containing the component A and the component B, and the component A of the acid is selected from the following structural formula ( One or two or more compounds of the group consisting of 1), (2), (5) to (7) and (14), and the B component of the acid is selected from the following structural formulas (19), (23), ( 25), one or two or more compounds of the group consisting of (35) to (37), (39), (44), and (49), wherein the amine component separately contains the component A or two of the component A and the component B. The component A of the amine is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12), ( One or two or more compounds of the group consisting of V-33) and (VII-2), the component B of the amine is selected from the group consisting of the following general formulae (VIII-2), (VIII-4), (VIII- One of the groups consisting of 5), (VIII-6), (XI-2), and (XI-4) The compound represented by the above formula, the alkenyl-substituted nadic acid ylidene imide compound comprises one or more compounds represented by the following structural formula (I na-1) to (I na-3), a heterocyclic compound Having one or more selected from the group consisting of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxazine The heterocyclic structure.

In the formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or a carbon number of 1. ~20 alkyl.

[18] The liquid crystal alignment agent according to [17], wherein the acid A component is a compound represented by the structural formula (1), and the acid B component is represented by the structural formula (19). The compound A, the A component 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 a pass. One or two or more compounds represented by the formulae (VIII-5), (XI-2) and (XI-4), the alkenyl-substituted nadic acid ylidene imine compound is represented by the structural formula (I na-1) a compound, the heterocyclic compound comprising a compound selected from the group consisting of 4,4'-methylenebis(N,N-diglycidylaniline), (3-glycidoxypropyl)trimethoxynonane, (3-glycidol) Oxypropyl)methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, bis[(3-ethyl-3-epoxypropenylmethoxy) Methyl]benzene, 2,4,6-tris(1'-aziridine)-1,3,5-triazine, N,N,N',N'-tetrathiopyranylmethyl-4, 4'-Diaminodiphenylmethane, poly(styrene-co-2-isopropenyloxazoline), and bis(3-phenyl-3,4-dihydro-2H-1,3- Bing oxazin-6-yl) consisting of a group of two or more compounds of methane.

[19] A liquid crystal alignment film obtained by calcining a liquid crystal alignment film according to the above [1] to [18] in a state of a film.

[20] A liquid crystal display device comprising a pair of substrates disposed in opposite directions, an electrode formed on one surface or both surfaces of a pair of substrates, and a liquid crystal alignment film formed on each of the pair of substrates A liquid crystal display element of a liquid crystal layer formed between a pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to [19].

According to the present invention, it is possible to provide a liquid crystal display element of various driving methods in which the ion density is high and the long-term reliability with respect to the ion density is improved over a long period of time.

The liquid crystal alignment agent of the present invention is a composition comprising: an alkenyl-substituted nadic acid ruthenium imine compound and having an oxirane selected from the group consisting of oxirane, oxetane, and thiirane a combination of one or more heterocyclic compounds of a heterocyclic structure consisting of aziridine, oxazoline, and oxazine, and a polyamine derivative and a derivative thereof One or more polymers of the substance.

<1. Alkenyl-substituted nadic acid ylide imide compound of the present invention>

The alkenyl-substituted nadic acid ruthenium imide compound used in the present invention will now be described. The above alkenyl-substituted nadic acid ylidene imide compound is preferably a compound which is soluble in a solvent which dissolves the polyglycine or its derivative used in the present invention and a heterocyclic compound. The compound represented by the following formula (I na) is exemplified as the alkenyl-substituted nadic ylidene imide compound.

In the formula (I na), R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or benzyl group. Base, n represents an integer from 1 to 2.

Further, in the general formula (I na), when n=1, R ³ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzyl group. _Let -(C _q H _2q )-O _t -(C _r H _2r O) _u -C _s H _2s+1 (q, r, s represent integers from 2 to 6, respectively, t represents 0 or 1, u represents 1 to 30 The polyoxyalkylene alkyl group, -(R) _v -C ₆ H ₄ -R ⁴ (v represents 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents hydrogen Or a group represented by an alkyl group having 1 to 4 carbon atoms, and -C ₆ H ₄ -T-C ₆ H ₅ (T represents -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, - The group represented by S- or -SO ₂ -) or a group in which one to three hydrogens directly bonded to the aromatic ring of these groups are substituted with a hydroxyl group.

Further, in the formula (I na), when n = 2, R ³ represents an alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and -(C _q H _2q O) _t - (C _r H _2r 0) _u -C _s H _2s -(q, r, s represent an integer of 2 to 6, respectively, t represents 0 or 1, u represents an integer from 1 to 30) Arylene having a carbon number of 6 to 12, and -(R) _v -C ₆ H ₄ -R ⁵ - (v represents 0 or 1, and R and R ⁵ respectively represent a hydrocarbon having 1 to 4 carbon atoms; a group represented by a ring or a cycloalkyl group having 5 to 8 carbon atoms, and -C ₆ H ₄ -T-C ₆ H ₄ - (T represents -CH ₂ -, -C(CH ₃ ) ₂ -, - a group represented by CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ O-, -S-, or -SO ₂ -), or an aromatic ring of these groups One to three hydrogens directly bonded are substituted with a hydroxyl group.

The above alkenyl-substituted nadic acid ylidene imide compound, for example, as described in Japanese Patent No. 2729565, can be used by substituting an alkenyl group for a nadic acid anhydride derivative with a diamine at 80 to 220 ° C. The compound obtained by the synthesis is maintained at a temperature of 0.5 to 20 hours, and a commercially available compound. Specific examples of the alkenyl-substituted nadic acid ylide imide compound include the compounds shown below.

N-Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-methylallylmethylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine, N-methylmethylallyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-methylmethylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2-ethylhexyl)allylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-(2-ethylhexyl)allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl- Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Formamidine, N-isopropenyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl -allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl-allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-phenyl-allyl bicyclo [ 2.2.1]hept-5-ene-2,3-dimethylimine, N-phenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine, N-benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-benzyl-allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine, N-benzyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2 '-Hydroxyethyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2'-hydroxyethyl)allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, N-(2'-hydroxyethyl)methylallylbicyclo[2.2.1]hept-5-ene-2,3-di Formamidine, N-(2',2'-dimethyl-3'-hydroxypropyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N (2',2'-Dimethyl-3'-hydroxypropyl)allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2' ,3'-dihydroxypropyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2',3'-dihydroxypropyl) ally Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-(3'-hydroxy-1'-propenyl)allylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine, N-(4'-hydroxycyclohexyl)allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine , N-(4'-hydroxyphenyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4'-hydroxyphenyl)allyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4'-hydroxyphenyl)methylallylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine, N-(4'-hydroxyphenyl)methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N -(3'-hydroxyphenyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(3'-hydroxyphenyl)allylmethylbicyclo [2.2.1]Hept-5-ene -2,3-dimethylimine, N-(p-hydroxybenzyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2'- (2'-Hydroxyethoxy)ethyl}allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2'-(2'-hydroxyethoxy Ethyl}allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2'-(2'-hydroxyethoxy)ethyl} Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine, N-{2'-(2'-hydroxyethoxy)ethyl}methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-[2'-{2'-(2"-hydroxyethoxy)ethoxy}ethyl] Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine, N-[2'-{2'-(2"-hydroxyethoxy)ethoxy}ethyl Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-[2'-{2'-(2"-hydroxyethoxy)ethoxy }ethyl]methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{4'-(4'-hydroxyphenyl isopropylidene)benzene Allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Imine, N-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine , N-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, and Oligomers of these compounds; N,N'-extended ethyl bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-Extension B Bis-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-extended ethyl bis(methylallylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine), N,N'-trimethylenebis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino), N,N'-hexamethylene bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-hexamethylene Bis (allylmethylbicyclo[2.2.1]-5-ene-2,3-dimethylimine), N,N'-dodecyl bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), N,N'-dodecyl bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -dimethylimine), N,N'-ring extension Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-cyclohexyl bis(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine), 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylidene Amine) propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)propoxy} Ethane, 1,2-bis{3'-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}ethane, bis[2 '-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}ethyl]ether, bis[2'-{3'- (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}ethyl]ether, 1,4-double {3'-(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine imine)propoxy}butane, N,N'-p-phenylene bis(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-p-phenylene bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine imine), N,N'-meta-phenyl bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine, N, N'-meta-phenyl bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-{(1 -methyl)-2,4-phenylene}bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-xylylene Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-xylylene bis(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine), N,N'-m-xylylenebis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine), N,N'-m-xylylenebis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), 2,2 - bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2-double [4'-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2-double [ 4'-{4'-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Oxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, double {4-(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine Phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, double {4-(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}anthracene, Double {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}indole, bis{4-(methylallylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)phenyl}indole, 1,6-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Formamidine)-3-hydroxyhexane, 1,1 2-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-3,6-dihydroxydodecane, 1,3-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-5-hydroxycyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine imine)propoxy}-3-hydroxypentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine)-2-hydroxybenzene, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2, 5-dihydroxybenzene, N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N' -m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-inter (2-hydroxyl) Benzyl-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-(2,3-dihydroxy) Benzyl-bis(allylbicyclo[2.2.1]hept-5- -2,3-dimethylimine), 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine -2'-hydroxyphenoxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)-2- Hydroxyphenyl}methane, bis{3-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)-4-hydroxyphenyl}ether, double {3-( Methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-5-hydroxyphenyl}indole, 1,1,1-tris{4'-(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine]}phenoxymethylpropane, N,N',N"-tris(vinylmethylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)isocyanurate, oligomers of these compounds, and the like.

Further, the alkenyl-substituted nadic acid ylidene imide compound used in the present invention may be a compound represented by the following structural formula containing an asymmetric alkylene group and a pendant phenyl group.

In the above-described alkenyl-substituted nadic acid ylidene imide compound to be used in the present invention, an alkenyl-substituted nadic acid ruthenium imide compound such as these may be used alone or as a mixture of two or more of these compounds.

Preferred examples of the above alkenyl-substituted nadic acid ylidene imide compound include the following compounds.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-dodecyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-cyclohexyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N '-Cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N-p-phenylene-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethyl sulfonate ), N, N'-p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-meta-strand Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-m-Benzyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-m-xylylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-bis[4'-{4'-(allylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2 Bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, double {4- (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) phenyl }ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)phenyl}indole, bis{4-(allylmethylbicyclo[ 2.2.1]hept-5-ene-2,3-carboximine)phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3 - dimethyl quinone imine) phenyl} hydrazine.

As the above alkenyl-substituted nadic acid ylidene imide compound, preferred compounds include the following compounds.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-dodecyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine), N,N'-cyclohexyl-bis(allylbicyclo[2.2.l]hept-5-ene-2,3-dimethylimine), N,N '-cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethyl oxime ), N, N'-p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-meta-strand Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine), N,N'-{(1-methyl)-2,4-phenylene} bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -dimethylimine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N , N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-bis[4'-{4'-(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine imine)phenoxy}phenyl]propane, 2,2- [4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}phenyl]propane, double {4-( Allyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5- Aceene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) benzene Methyl methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane.

The compound which is more preferable than the above-mentioned alkenyl-substituted nadic acid ylidene imide compound is exemplified by the double {4-(allylbicyclo[2.2.1]g- represented by the following structural formula (I na-1). 5-ene-2,3-dimethylimine)phenyl}methane, N,N'-meta-phenyl-bis(allylbicyclo[2.2] represented by the following structural formula (I na-2) .1]hept-5-ene-2,3-dimethylimine), and N,N'-hexamethylene-bis(allylbicyclo) represented by the following structural formula (I na-3) [2.2.1] Hept-5-ene-2,3-dimethylimine).

<2. Heterocyclic compound used in the present invention>

The heterocyclic compound used in the present invention has a group selected from the group consisting of oxirane, oxetane, thiirane, aziridine, and oxazoline. One or more heterocyclic structures. The heterocyclic compound may be one compound having the above heterocyclic structure, or may be two or more compounds. One of the aforementioned heterocyclic compounds may have only one heterocyclic ring structure or may have two or more kinds of heterocyclic structures. Further, one of the aforementioned heterocyclic compounds may have one of the aforementioned heterocyclic structures, but preferably has two or more of the above heterocyclic structures.

Further, the heterocyclic compound may be a polymer having a heterocyclic structure in a side chain, or may be a copolymer. The polymer having a heterocyclic structure in the side chain length may be a homopolymer of a monomer having a heterocyclic structure in a side chain, or a monomer having a heterocyclic structure in a side chain and having no heterocyclic structure. Copolymer of monomer. The copolymer having a heterocyclic structure in a side chain may be a copolymer of two or more kinds of monomers having a heterocyclic structure in a side chain, or may be a monomer having two or more kinds of monomers having a heterocyclic structure in a side chain. A copolymer of a monomer having a heterocyclic structure.

The aforementioned heterocyclic structure has a hetero atom. The reason why the liquid crystal alignment agent containing the above heterocyclic compound suppresses the ion density and the long-term stability thereof is not clear, but it is generally considered that the hetero atom in the heterocyclic structure and the carbonyl group in the poly-proline are in the above heterocyclic compound. The reaction is related to the distribution of the heterocyclic compound (biasing to the surface of the film and its vicinity) in the film when the liquid crystal alignment film is formed. Therefore, the above heterocyclic compound is, for example, preferably having a structure in which a hetero atom in the heterocyclic structure can react with a carbonyl group of polyphthalic acid to cause these effects.

The heterocyclic compound mainly having ethylene oxide (oxirane) as a heterocyclic ring structure (hereinafter, also referred to as "oxirane compound"), mainly having oxetane as a hetero ring, is used in the present invention. a heterocyclic compound having a ring structure (hereinafter also referred to as "oxetane compound"), a heterocyclic compound mainly having a thiirane as a heterocyclic ring structure (hereinafter, also referred to as "thiirane" a compound"), a heterocyclic compound mainly having aziridine as a heterocyclic structure (hereinafter also referred to as "aziridine compound"), and a heterocyclic oxazoline as a heterocyclic structure The cyclic compound (hereinafter also referred to as "oxazoline compound") is preferably soluble in a solvent which dissolves the polyamine or the derivative thereof used in the present invention.

Examples of the oxetane compound include bis[(3-ethyl-3-epoxypropenylmethoxy)methyl]benzene and bis[(3-ethyl-3-epoxypropane). Methoxy)methylphenyl]methane, bis[(3-ethyl-3-epoxypropenylmethoxy)methylphenyl]ether, bis[(3-ethyl-3-epoxypropane) Methoxy)methylphenyl]propane, bis[(3-ethyl-3-epoxypropenylmethoxy)methylphenyl]indole, bis[(3-ethyl-3-epoxypropane) Methoxy)methylphenyl]one, bis[(3-ethyl-3-epoxypropenylmethoxy)methylphenyl]hexafluoropropane, tris[(3-ethyl-3-cyclo) Oxypropanylmethoxy)methyl]benzene, and tetrakis[(3-ethyl-3-epoxypropenylmethoxy)methyl]benzene. Other examples include oligomers and polymers having an oxypropylene group.

Examples of the thiirane compound include phenyl chlorohydrinyl ether, butyl chlorohydrinyl ether, and 3, 3 according to the method described in J. Org. Chem., 28, 229 (1963). , 3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, N-decahydrate quinone imine, (nonafluoro-N-butyl) epoxide, perfluoro Ethyl chlorohydrin ether, epichlorohydrin, epibromohydrin, N,N- sulphate aniline, and 3-[2-(perfluorohexyl)ethoxy]-1,2-ring Oxypropane, ethylene glycol hexahydroglycidyl ether, polyethylene glycol hexahydroglycidyl ether, propylene glycol hexahydroglycidyl ether, tripropylene glycol hexahydroglycidyl ether, polypropylene glycol hexahydroglycidyl ether, Neopentyl glycol hexahydroglycidyl ether, 1,6-hexanediol hexahydroglycidyl ether, glyceryl succinyl ether, 2,2-dibromoneopentyl glycol hexahydroglycidyl ether, And 3-(N,N-dihydroglycidyl)aminopropyltrimethoxydecane, 1,3,5,6-tetrahydroglycidyl-2,4-hexanediol, N,N,N ',N'-SiXu hydroglyceryl-m-xylenediamine, 1,3-double (N,N Diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and 3-(N-allyl -N-glycidyl) The glycidyl group in the aminopropyltrimethoxydecane is substituted with sulfur, and the glycidyl group is substituted with a compound of an ethylene sulfide group.

The aziridine compound may, for example, be 2,4,6-tris(1'-aziridine)-1,3,5-triazine or ω-aziridinepropionic acid-2,2- Dihydroxymethylheptanol triesters, 2,4,6-tris(2-methyl-1-aziridine)-1,3,5-triazine, 2,4,6-tris(2-B 1,-1-aziridinyl)-1,3,5-triazine, 4,4'-bis(vinylimidocarbonylamino)diphenylmethane, bis(2-ethyl-1-nitrogen Propidyl)benzene-1,3-dimethylamine, tris(2-ethyl-1-aziridine)benzene-1,3,5-trimethylammonium, bis(2-ethyl-1- Aziridine) sebacate, 1,6-bis(vinylimidocarbonylamino)hexane, 2,4-diethylethylurea toluene, 1,1'-carbonyl-double extension Ethylimine, polymethylene-diethylurea (C2~C4), and N,N'-bis(4,6-diethylethylamine-1,3,5-triazine-2 -yl) hexamethylenediamine and the like. Other examples include oligomers and polymers having an aziridine group.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris(2-oxazolinyl-2)benzene, and 4-furan-2-yl. Methylene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-di Hydrogen-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxo Oxazoline, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2, 2'-methylenebis(4-phenyl-2-oxazoline) and the like. Other examples include polymers and oligomers having an oxazolyl group such as EPOCROS (trade name: manufactured by Nippon Shokubai Co., Ltd.).

Examples of the oxirane compound include a glycidyl ether type oxirane compound, a fatty cyclic oxirane compound, a glycidyl ester type oxirane compound, and a glycidyl amine type ring. An oxyethane compound, a heterocyclic oxirane compound, an oxirane group-containing acrylic compound, a decane type oxirane compound, or the like.

Examples of the commercially available product of the glycidyl ether type oxirane compound include Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, and Epikote 1010 (manufactured by Yuka Shell Epoxy Co., Ltd.). Epikote 807 (manufactured by Yuka Shell Epoxy Co., Ltd.), which is commercially available as a fatty cyclic oxirane compound, such as CY-175, CY-177, CY-179 (manufactured by CIBA-GEIGY Co., Ltd.), ERL-4234, ERL-4299, ERL-4221, and 4206 (manufactured by UCC); commercially available as a glycidyl ester type oxirane compound, for example: 508 (Showa Denko Co., Ltd.), Araldit CY-182, Araldit CY-192, Araldit CY-184 (manufactured by CIBA-GEIGY Co., Ltd.), EPICLON 200, EPICLON 400 (Dainippon Ink Co., Ltd.), Epikote 871, Epikote 872 (manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.); as a glycidylamine-type oxirane compound, for example, tetraglycidyldiaminodiphenyl Methane, triglycidyl p-aminophenol, triglycidyl m-amino phenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidyl meta-xylylene diamine, diglycidyl Tribromoaniline, tetraglycidyl bisaminomethylcyclohexane; commercially available as a heterocyclic oxirane compound, such as Araldit PT810 (manufactured by CIBA-GEIGY Co., Ltd.), Epikote RXE-15 (Yuka Shell Epoxy ( (Shares)), EPITEC (manufactured by Nissan Chemical Co., Ltd.); as an acrylic compound containing an oxirane group, a radically polymerizable compound having an oxiranyl group may be used alone or/and other radicals The polymerizable compound is obtained by radical polymerization in a solvent. Examples of the radical polymerizable compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-n-propyl acrylate glycidol. Base ester, α-n-butyl acrylate glycidyl ester, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyhexyl acrylate , -6,7-epoxyhexyl methacrylate, α-ethyl acrylate-6,7-epoxyhexyl ester, N-[4-(2,3-epoxypropoxy)-3,5- Dimethylbenzyl] decylamine acrylate, N-[4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl] decylamine acrylate, and the like.

Further, many of the oxirane compounds exemplified herein are high molecular weight bodies, but the oxirane compound used in the present invention is not limited by molecular weight, and for example, bisphenol A or bisphenol F may also be used. A diglycidyl ether-like low molecular weight body. Among them, in the case of a low molecular weight body, there is a possibility of elution into the liquid crystal, and therefore a high molecular weight body is preferred.

Examples of the decane-type oxirane compound include (3-glycidoxypropyl)trimethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane, and 2-( 3,4-epoxycyclohexyl)ethyltrimethoxydecane, 5,6-epoxyhexyltriethoxydecane, (3-glycidoxypropyl)dimethylethoxydecane, (3- Glycidoxypropyl)methyldiethoxydecane, and the like.

In order to make the effect of the oxirane group remarkable, a catalyst can also be added to the oxirane compound used in the present invention.

Examples of the co-catalyst include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, anthracene, carbazole, benzoimidazole, and iso-cyanuric acid. 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"-diamino Imidazole derivatives such as triazinyl)imidazole and benzoimidazole are preferred. These catalysts may be used singly or in combination of two or more kinds. In general, it is preferably used in a proportion of 0.01 to 10 parts by weight based on the total amount of the oxirane compound (in terms of total amount).

The oxazine compound to be used in the present invention is, for example, a compound represented by the following general formulae (a) to (f), but is not particularly limited thereto.

In the general formulae (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 respectively represented. Hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, X represents a single bond, -O-, -S-, -S-S-, -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-, m represents 1~ An integer of 6.

Further, in the general formulae (e) and (f), Y independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or An alkyl group having 1 to 3 carbon atoms. In the general formulae (a), (b), (c), (d), (e), and (f), hydrogen bonded to a benzene ring or a naphthalene ring may be independently substituted into -F, -CH ₃ , -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ .

Further, the oxazine compound used in the present invention comprises an oligomer and a polymer having an oxazine structure in a side chain, an oligomer having a oxazine structure in a main chain, and a polymer.

The oxazine compound represented by the formula (a) includes, for example, an oxazine compound represented by the following structural formula and formula.

In the formula (a-2), R ^{1 is} preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (b) includes, for example, an oxazine compound represented by the following structural formula and formula.

In the general formulae (b-2), (b-8), and (b-10), R ^{1 is} preferably independently an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. alkyl.

The oxazine compound represented by the formula (c) includes, for example, an oxazine compound represented by the following structural formula and formula.

In the general formulae (c-2), (c-4), (c-6), (c-8), (c-10), and (c-12), R ^{1 is} preferably a carbon number of 1 to 30. The alkyl group is more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (d) includes, for example, an oxazine compound represented by the following structural formula.

[化23]

The oxazine represented by the formula (e) is, for example, an oxazine compound represented by the following structural formula.

The oxazine represented by the formula (f) is, for example, an oxazine compound represented by the following structural formula.

Among these, it is better to cite structural formulas (b-1), (c-1), (c-3), (c-5), (c-7), (c-9), ( D-1) The oxazine compound represented by (d-6), (e-3), (e-4), (f-2) to (f-4).

The oxazine compound can be produced, for example, by the same method as the method described in WO2004/009708, JP-A-H11-12-258, and JP-A-2004-352670.

<3. Polylysine or derivative thereof used in the present invention>

The polyaminic acid or a derivative thereof used in the present invention is dissolved in a solvent when it is prepared into a liquid crystal alignment agent to be described later, and when the liquid crystal alignment agent is formed into a liquid crystal alignment film described later, it can be formed into a polysiloxane. A component of a liquid crystal alignment film containing an amine as a main component. Examples of such a polyamic acid or a derivative thereof include polyglycine, soluble polyimine, polyphthalate, and polyamine amide. More specifically, (1) polyimine formed by dehydration ring-closing reaction of all amine groups of polyproline and carboxyl groups, and (2) partial polyazide formed by partial dehydration ring-closing reaction The amine, (3) the carboxyl group of the polyproline is converted into an ester polyester, and (4) a part of the acid dianhydride contained in the tetracarboxylic dianhydride compound is substituted with an organic dicarboxylic acid to obtain a reaction. The polyamidamine-polyamide copolymer and (5) a polyamidoquinone imide formed by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyglycine or a derivative thereof used in the present invention may be one of these components, or may be two or more components.

The polyamic acid or a derivative thereof is preferably a polyamic acid obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. In the present invention, such a polyaminic acid can be used.

The polyamic acid or a derivative thereof can be obtained by a reaction of a tetracarboxylic dianhydride with a diamine. In the tetracarboxylic dianhydride of the present invention, one or two or more kinds of tetracarboxylic dianhydrides may be used, but a part of the tetracarboxylic dianhydride may be substituted with a dicarboxylic acid. Here, the ratio of the dicarboxylic acid to the tetracarboxylic dianhydride is preferably 10 mol% or less.

As the diamine of the present invention, one or two or more kinds of diamines may be used, but a part of the diamine may be substituted with a monoamine. Here, it is preferred to set the ratio of the monoamine to the diamine to 10 mol% or less.

The above tetracarboxylic dianhydride can be optionally used by using one or two or more compounds. When two or more tetracarboxylic dianhydrides are used, it is preferred to use an aromatic tetracarboxylic dianhydride as the A component of the acid, and an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride. One or two components B as an acid. For these tetracarboxylic dianhydrides, one or two or more compounds may be used, respectively.

Further, in order to use the polyglycolic acid of the present invention as a component of the liquid crystal alignment agent, it is preferred to be in a form soluble in a solvent. In order to prepare the polylysine of the present invention into the soluble form, it is preferred to appropriately select the tetracarboxylic dianhydride used as the acid component.

Here, as the aromatic tetracarboxylic dianhydride which is used as the component A of the acid, for example, acid dianhydride represented by the following structural formulas (1) to (18) is exemplified. Among the following aromatic tetracarboxylic dianhydrides, acid dianhydrides represented by structural formulas (1), (2), (5), (6), (7), and (14) are more preferable. Most preferably, the pyromellitic dianhydride represented by the structural formula (1) is used.

In addition, as the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride which are used as the component B of the acid, for example, acid dianhydride represented by the following structural formulas (19) to (67) can be specifically exemplified.

Among the above tetracarboxylic dianhydrides, acid dianhydrides represented by structural formulas (19) to (39) and (49) are preferably mentioned, and structural formulas (19) and (23) are more preferably used. And the acid dianhydride represented by (25), (35) to (37), (39), (44) and (49), particularly preferably 1,2 represented by the structural formula (19). 3,4-cyclobutane tetracarboxylic dianhydride.

Further, in order to form the polylysine of the present invention or a derivative thereof into a solvent-soluble polyimine, it is preferred to use structural formulas (24), (35) to (44), (49). And the acid dianhydride represented by (50), (53) and (60).

In the tetracarboxylic dianhydride of the present invention, the tetracarboxylic dianhydride represented by the structural formulae (1) to (67) may be used alone, or two or more of them may be used in combination. Aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride (especially preferably pyromellitic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid) a liquid crystal alignment film which is formed by a liquid crystal alignment agent comprising a polyamic acid synthesized from the tetracarboxylic dianhydride of the present invention, and which can be provided to a liquid crystal display element comprising the liquid crystal alignment film. Particularly good ion density.

Further, the tetracarboxylic dianhydride of the present invention may be a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the structural formulae (1) to (67). The other tetracarboxylic dianhydride is arbitrary, and for example, a tetracarboxylic dianhydride having a side chain structure may also be mentioned. The following liquid crystal alignment film of a tetracarboxylic dianhydride having a side chain structure can be used to increase a pretilt angle in a liquid crystal display element comprising the liquid crystal alignment film, which is used by the tetracarboxylic acid comprising the present invention. It is formed by a liquid crystal alignment agent of polyphthalic acid synthesized by acid dianhydride.

The tetracarboxylic dianhydride having a side chain structure is not particularly limited, but in the present invention, a compound having a steroid skeleton represented by the following structural formulae (68) and (69) can be preferably used.

Further, the other tetracarboxylic dianhydride which can be used in the tetracarboxylic dianhydride of the present invention is not limited to the tetracarboxylic dianhydride having a side chain structure, and of course, within the scope of achieving the object of the present invention, Other various forms of tetracarboxylic dianhydride are present. Further, the other tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Further, a part of the tetracarboxylic dianhydride used in the tetracarboxylic dianhydride of the present invention may be substituted with an carboxylic acid anhydride. By substituting a part of the tetracarboxylic dianhydride into a carboxylic acid anhydride, the termination of the polymerization reaction can be caused, and the progress of the above reaction can be suppressed, so that the molecular weight of the obtained polymer (polyproline) can be easily controlled. The ratio of the carboxylic anhydride to the tetracarboxylic anhydride does not impair the effects of the present invention. However, as a standard, it is preferably 10 mol% or less of the total amount of the tetracarboxylic dianhydride.

As described above, the polyphthalic acid contained in the liquid crystal alignment agent of the present invention is a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine.

The diamine used in the present invention may be arbitrarily selected from one or two or more compounds. For the diamine, for example, a linear diamine may be used alone as the component A, and the diamine of the component A may be used in combination with the diamine having a side chain structure as the component B. When two or more diamines are used, for example, it is preferred to use a linear diamine as the A component of the amine and a diamine having a side chain structure as the B component of the amine. For these diamines, one or two or more compounds may be used separately.

The diamine which is the component A of the above-mentioned amine may be arbitrarily selected as the diamine having no side chain structure, and preferably the diamine represented by the general formulae (I) to (VII).

H ₂ N-A ¹ -NH ₂ (I)

In the formula (I), A ¹ represents -(CH ₂ ) _m -. Here, m represents an integer from 1 to 12. Further, in the general formulae (III), (V), and (VII), A ¹ independently represents a single bond, -O-, -S-, -S-S-, -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-. Here m independently represents an integer from 1 to 12. Further, in the formula (VI), A ² independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or a carbon number of 1. ~6 alkylene. Further, the hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulae (II) to (VII) can also be independently substituted into -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl.

Examples of the diamine represented by the formula (I) include diamines represented by the structural formulae (I-1) to (I-4).

Examples of the diamine represented by the formula (II) include diamines represented by the structural formulae (II-1) and (II-2).

Examples of the diamine represented by the formula (III) include diamines represented by the structural formulae (III-1) to (III-3).

Examples of the diamine represented by the formula (IV) include diamines represented by the structural formulae (IV-1) to (IV-16).

The diamine represented by the formula (V) is, for example, a diamine represented by the structural formulae (V-1) to (V-34).

Examples of the diamine represented by the formula (VI) include diamines represented by the structural formulae (VI-1) to (VI-6).

The diamine represented by the formula (VII) includes, for example, a diamine represented by the structural formulae (VII-1) to (VII-16).

Among these, structural formulae (IV-1) to (IV-5), (IV-15), (IV-16), (V-1) to (V-12), (V) are preferred. -26), (V-27), (V-31), (V-33), (VI-1), (VI-2), (VI-6), (VII-1)~(VII-5 The diamine represented by the formula (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12) is preferably exemplified. , the diamine represented by (V-33), (VII-2).

The diamine of the present invention may be used alone or in combination of two or more kinds of the diamines represented by the above formulas (I) to (VII). The molar ratio of the diamine represented by the above formula (I) to (VII) in the diamine of the present invention may be selected according to the selected diamine represented by the above formula (I) to (VII). The structure and the desired ion density are adjusted, preferably from 1 to 100%, more preferably from 5 to 80%, based on the total amount of the diamine.

As described above, the diamine of the present invention may be one or two or more kinds of diamines, but in particular, a large pretilt angle is required, such as a VA type liquid crystal display element, an OCB type liquid crystal display element, an STN type liquid crystal display element, or the like ( In the use of the pretilt angle, it is preferred to use a diamine having a side chain structure as the component B of the amine.

In the present specification, the term "diamine having a side chain structure" means that when a substituent linking two amine groups is used as a main chain, a branch which generates a branch in the autonomous chain can exhibit a desired pretilt angle. a diamine of a base (side chain). That is, by reacting a diamine having a side chain structure with a tetracarboxylic dianhydride, it is possible to provide a polylysine or a polyimine (a branched polyamine) having a side chain group with respect to a polymer main chain. Acid or branched polyimine). Such a liquid crystal alignment film comprising a liquid crystal alignment agent having a polyamic acid or a polyimine having a side chain group with respect to a polymer main chain can increase a pretilt angle in the liquid crystal display element. . In this case, it is described in the above-mentioned Patent Document 1 (Japanese Patent Laid-Open Publication No. Hei 11-193345).

Therefore, the side chain in the diamine having a side chain structure can be appropriately selected depending on the desired pretilt angle. For example, it is preferred that the side chain has a carbon number of 3 or more. Specific examples thereof include (1) a phenyl group which may have a substituent, a cyclohexylphenyl group which may have a substituent, a bis(cyclohexyl)phenyl group which may have a substituent, or a carbon number of 3 or more. An alkyl group, an alkenyl group or an alkynyl group, (2) a phenoxy group which may have a substituent, a cyclohexyloxy group which may have a substituent, a bis(cyclohexyl)oxy group which may have a substituent, a phenyl group which may have a substituent a cyclohexyloxy group, a cyclohexylphenoxy group which may have a substituent, or an alkoxy group having 3 or more carbon atoms, an alkenyloxy group or an alkynyloxy group, a (3) phenylcarbonyl group, or an alkyl group having 3 or more carbon atoms a carbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group, (4) a phenylcarbonyloxy group, or an alkylcarbonyloxy group having at least 3 carbon atoms, an alkenylcarbonyloxy group or an alkynylcarbonyloxy group, (5) may have a substitution a phenyloxycarbonyl group, a cyclohexyloxycarbonyl group which may have a substituent, a bis(cyclohexyl)oxycarbonyl group which may have a substituent, a bis(cyclohexyl)phenyloxycarbonyl group which may have a substituent, a cyclohexyl bis(phenyl)oxycarbonyl group having a substituent or an alkyloxycarbonyl group having at least 3 carbon atoms, an alkenyloxycarbonyl group or an alkynyloxycarbonyl group And (6) a phenylaminocarbonyl group, or an alkylaminocarbonyl group having 3 or more carbon atoms, an alkenylaminocarbonyl group or an alkynylaminocarbonyl group, (7) a cyclic alkyl group having 3 or more carbon atoms, (8) a cyclohexylalkylene group which may have a substituent, a phenylalkylene group which may have a substituent, a bis(cyclohexyl)alkylene group which may have a substituent, a cyclohexylphenylalkylene group which may have a substituent, may have a bis(cyclohexyl)phenylalkylene group of a substituent, a phenylalkyloxy group which may have a substituent, an alkylphenyloxycarbonyl group, or an alkylbiphenyloxycarbonyl group, (9) an alkyl group, a fluorine-substituted alkyl group, or an alkoxy-substituted phenyl group, or a cyclohexyl group, and (10) two or more benzene rings or cyclohexane rings are bonded by a single bond, or via -O-, -COO-, - OCO-, -CONH- or an alkyl group bonded to an alkyl group having 1 to 3 carbon atoms, a monofluoroalkyl group, or a ring group substituted with an alkoxy group, or a group having a steroid skeleton, etc., but not Limited to these bases.

Here, examples of the "substituent group" include an alkyl group, an alkoxy group, or an alkoxyalkyl group.

Alternatively, bis(cyclohexyl) or bis(phenyl) may be interrupted by an alkyl group.

Further, in the present specification, in the case of "alkyl group", "alkenyl group" or "alkynyl group", it may be linear or branched.

Specific examples of the diamine having a side chain structure used in the present invention include diamines represented by the following general formulae (VIII) to (XII).

In the formula (VIII), R ¹ represents 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 formula (XIII), an alkyl group having 1 to 30 carbon atoms, or a phenyl group; And when the carbon number of the alkyl group is 2 or more, any -CH ₂ - thereof may be independently substituted by -O-, -CH=CH- or -C≡C- (wherein the oxygen is discontinuous), and then the benzene The hydrogen of the group may also be independently substituted by fluorine, methyl, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy, except that -R ¹ -R ² represents a benzyl group.

In the formula (IX), R ³ independently represents hydrogen or a methyl group; R ⁴ represents hydrogen or an alkyl group having 1 to 30 carbon atoms; and R ⁵ independently represents a single bond, -CO- or -CH ₂ -.

In the formula (X), R ³ independently represents hydrogen or a methyl group; R ⁴ represents hydrogen or an alkyl group having 1 to 30 carbon atoms; and R ⁵ independently represents a single bond, -CO- or -CH ₂ -; R ⁶ And R ⁷ each independently represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group.

In the formula (XI), R ⁸ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group having 2 or more carbon atoms may be independently -O-, -CH=CH. - or -C≡C-substitution (wherein the oxygen is discontinuous); R ⁹ independently represents -O- or an alkylene group having 1 to 6 carbon atoms; and ring A represents a 1,4-phenylene group or a 1,4-ring group Extending a base; a means 0 or 1; b means 0, 1 or 2; c independently represents 0 or 1.

In the formula (XII), R ¹⁰ represents an alkyl group having 3 to 30 carbon atoms or a monofluoroalkyl group having 3 to 30 carbon atoms; and R ¹¹ represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or a carbon number of 1 a monofluorinated alkyl group of ~30; R ¹² independently represents -O- or an alkylene group having 1 to 6 carbon atoms; and d independently represents 0 or 1.

In the formula ( ^XIII ), R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and carbon. a 1-3 alkyloxyalkyl group (wherein the oxygen is discontinuous), or a C 1 to 3 alkyloxy group (wherein the oxygen is discontinuous); and R ¹⁶ and R ¹⁷ independently represent hydrogen, fluorine or methyl R ¹⁸ represents hydrogen, fluorine, chlorine, cyano, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a monofluoromethyl group, and 2 a fluoromethyl group, a trifluoromethyl group, a monofluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group; any of the aforementioned alkyl group, alkoxy group and alkoxyalkyl group having a carbon number of 2 or more - CH ₂ - may also be substituted by difluoromethylene or by a group represented by the following formula (X IV); ring B and ring C each independently represent 1,4-phenylene or 1,4-cyclode. Hexyl; 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 total of these values is 1 or more; and l and m each independently represent 1 or 2.

In the formula (X IV), R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 1 to 100.

Further, in the formula (IX), hydrogen bonded to the carbon forming the steroid skeleton may be independently substituted with -CH ₃ .

The diamine represented by the formula (VIII) may, for example, be a diamine represented by the following formula or structural formula (VIII-1) to (VIII-43).

[化42]

In the general formulae (VIII-1) to (VIII-11), R ²³ preferably represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably a carbon number of 5 to 25 An alkyl group or an alkoxy group having a carbon number of 5 to 25. Further, R ²⁴ preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

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

[化44]

In the general formulae (VIII-18) to (VIII-37), R ²⁷ preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably 3 to 30 carbon atoms. 25 alkyl or alkoxy having 3 to 25 carbon atoms. Further, R ²⁸ preferably represents -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , More preferably, it represents an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

Among these, a diamine represented by the general formulae (VIII-1) to (VIII-11) is preferred. More preferably, the diamines represented by the general formulae (VIII-2), (VIII-4), (VIII-5) and (VIII-6) are mentioned.

In the above formula (IX), it is preferred that one of the two "NH ₂ -Ph-R ⁵ -O-" is bonded to the 3-position of the steroid skeleton, and the other is bonded to the 6-position. Further, it is preferred that the two amine groups are bonded to the phenyl ring carbon, respectively, and the bonding position with respect to R ⁵ is bonded to the meta or para position.

As the diamine represented by the formula (IX), for example, a diamine represented by the structural formula (IX-1) to (IX-4) can be obtained.

In the above formula (X), two "NH ₂ -(R ⁷ -)Ph-R ⁵ -O-" are bonded to the carbon of the phenyl ring, respectively, but preferably, relative to the steroid skeleton The bonded carbon is a meta or para carbon bond. Further, the two amine groups are bonded to the phenyl ring carbon, respectively, but it is preferred to bond to the meta or para position with respect to R ⁵ .

The diamine represented by the formula (X) is, for example, a diamine represented by the structural formulae (X-1) to (X-8).

[化47]

In the above formula (XI), the two amine groups are bonded to the carbon of the phenyl ring, respectively, and it is preferred to bond to the meta or para position with respect to R ⁹ .

Examples of the diamine represented by the formula (XI) include diamines represented by the formulae (XI-1) to (XI-8).

In the general formulae (XI-1) to (XI-3), R ²⁹ preferably represents -H, an alkyl group having 1 to 30 carbon atoms; and in the general formula (XI-4) to (XI-8), R ³⁰ More preferably, -H, an alkyl group having 1 to 20 carbon atoms.

In the above formula (XII), the two amine groups are bonded to the carbon of the phenyl ring, respectively, and it is preferably bonded to the meta or para position with respect to R ¹² .

The diamine represented by the formula (XII) may, for example, be a diamine represented by the formula (XII-1) to (XII-3).

In the general formulae (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.

The diamine of the present invention may be used alone or in combination of two or more kinds of the diamines represented by the above formulas (VIII) to (XII). The molar ratio of the diamine having a side chain structure in the diamine of the present invention can be adjusted according to the diamine structure having a selected side chain structure and a desired pretilt angle, preferably 1~100%, better 10~100%.

Further, the diamine of the present invention may be other than the diamine represented by the general formulae (I) to (VII) and the diamine having a side chain structure represented by the general formulae (VIII) to (XII). Other diamines. The other diamine is arbitrary, and examples thereof include a naphthalene-based diamine having a naphthalene structure, an anthracene-based diamine having a fluorene structure, or a decane-based diamine having a decane bond, or a formula ( a diamine of a side chain structure other than VIII)~(XII).

The dioxane-based diamine is not particularly limited, and a compound represented by the following formula (X V) can be preferably used as the diamine of the present invention.

In the formula (XV), R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and A ³ independently represents a methylene group, a stretched phenyl group or a stretched phenyl group substituted with an alkyl group. l represents an integer from 1 to 6, and m represents an integer from 1 to 10.

Further, the other diamine is not limited to the above-described alkoxy-based diamine. For example, a compound represented by the following general formulae (1') to (8') can be preferably used as the diamine of the present invention.

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

Further, the other diamines other than the general formulae (I) to (XII) used in the diamine of the present invention are not limited to the above-described oxane-based diamines, and of course, within the scope of achieving the object of the present invention. There are also various other forms of diamines. In addition, the other diamines may be used alone or in combination of two or more.

The diamine of the present invention can impart a suitable pretilt angle to the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention by appropriately selecting the kind of the diamine and the combination thereof.

In the case of a VA type liquid crystal display element, a large pretilt angle of about 80 to 90 degrees is often required; in the case of an OCB type liquid crystal display element, a pretilt angle of about 7 to 20 degrees is often required; in a TN type liquid crystal display In the case of an element and an STN type liquid crystal display element, a pretilt angle of about 3 to 10 degrees is often required; and in the case of an IPS type liquid crystal display element, a pretilt angle of about 0 to 3 degrees is often required. Therefore, the liquid crystal alignment agent of the present invention which can appropriately adjust the pretilt angle by using a diamine having a side chain structure can be applied to any type of liquid crystal display element.

As described above, a part of the diamine used in the diamine of the present invention may be substituted with a monoamine. By substituting a part of the diamine into a monoamine, the termination of the polymerization reaction can be caused, and the progress of the previous reaction can be suppressed, so that the molecular weight of the obtained polymer (polyproline) can be easily suppressed. The ratio of the monoamine to the diamine may vary within a range not impairing the effects of the present invention, and as a standard, it is preferably 10 mol% or less of the total amine amount.

The polyaminic acid or derivative thereof of the present invention may have any weight average molecular weight. The weight average molecular weight of the above polyamic acid or a derivative thereof is not particularly limited, but in the case of being used as a component of a liquid crystal alignment agent, it is preferably 5 × 10 ³ or more, more preferably 1 × 10 ⁴ the above. The polyglycine or a derivative thereof having a weight average molecular weight of 5 × 10 ³ or more does not evaporate in the step of calcining the liquid crystal alignment film, and thus has a preferable physical property as a component of the liquid crystal alignment agent.

Here, the weight average molecular weight of polylysine or a derivative thereof is measured by a gel permeation chromatography (GPC) method. For example, the obtained polyaminic acid or a derivative thereof is diluted with dimethylformamide (DMF) to a polyglycine or a derivative thereof at a concentration of about 1% by weight, and Chromatopac C-R7A (manufactured by Shimadzu Corporation) is used. DMF was used as a developing solvent and measured by a gel permeation chromatography (GPC) method, and polystyrene conversion was carried out to determine the weight average molecular weight of polylysine or a derivative thereof. Further, in order to carry out GPC measurement of polyacrylic acid, polyacrylic acid or the like with good precision, an inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid, and an inorganic salt such as lithium bromide or lithium chloride are dissolved in a DMF solvent. Solvent.

The polyaminic acid or a derivative thereof of the present invention can be produced by a known method. For example, one or two or more kinds of diamines represented by the general formulae (I) to (XII) are added to a reaction container having a raw material inlet, a nitrogen gas inlet, a thermometer, a stirrer, and a condenser, and are added as the case may be. One or more diamines selected from other diamines are further added as needed to the desired amount of monoamine.

Next, one or more of a solvent (for example, N-methyl-2-pyrrolidone and dimethylformamide as a guanamine-based polar solvent) and a tetracarboxylic dianhydride are charged, and further, if necessary, Carboxylic anhydride. In this case, the total amount of the tetracarboxylic dianhydride to be charged is preferably about the same as the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

A solution of polylysine can be obtained by reacting at a temperature of 0 to 70 ° C for 1 to 48 hours under stirring. Further, by heating to increase the reaction temperature (for example, 50 to 80 ° C), a polyglycine having a small molecular weight can also be obtained.

The polyglycolic acid of the present invention is precipitated by a large amount of a poor solvent, and the solid component is completely separated from the solvent by filtration or the like, and analyzed by IR or NMR, whereby it can be identified. Further, the solid polylysine is decomposed by a strong alkali aqueous solution such as KOH or NaOH, and then extracted with an organic solvent, and analyzed by GC, HPLC or GC-MS, whereby the monomer to be used can be identified.

For the solution of the obtained polyamic acid, in order to adjust it to a desired viscosity, it can be diluted with a solvent and used.

Further, in the case where the polylysine of the present invention is made into a soluble polyimine as a polyphthalic acid derivative, the polyaminic acid solution and acetic anhydride, propionic anhydride, and trifluorocarbon as a dehydrating agent can be used. An acid anhydride such as acetic anhydride or a tertiary amine such as triethylamine, pyridine or trimethylpyridine which is a dehydration ring-closing catalyst is obtained by carrying out a hydrazine imidization reaction at a temperature of 20 to 150 °C.

Alternatively, a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a glycol solvent) may be used to precipitate the polyamic acid from the polyaminic acid solution, and then the precipitated polylysine may be used. A solvent such as toluene or xylene is obtained by performing a ruthenium imidization reaction at a temperature of 20 to 150 ° C together with the same dehydrating agent and dehydration ring-closure catalyst as described above.

In the above hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (mole ratio). The total amount of the two used is preferably 1.5 to 10 moles per mole of the acid dianhydride contained in the tetracarboxylic dianhydride to be used. The degree of ruthenium iodization can be controlled by adjusting the chemical hydrazide dehydrating agent, the amount of the catalyst, the reaction temperature, and the reaction time, and a partial polyimine can be obtained.

The obtained polyimine is separated from the solvent, and may be formed by combining the alkenyl-substituted nadic acid ruthenium imide compound and at least one selected from the above heterocyclic compounds in a solvent to be described later. The modifier is used as a liquid crystal alignment agent, and may be used as a liquid crystal alignment agent, or may be added as a liquid crystal alignment agent without being separated from the solvent.

Further, as described above, a part of the acid dianhydride used in the tetracarboxylic dianhydride of the present invention may be substituted with an organic dicarboxylic acid. When the polydiamine acid of the present invention is produced using an organic dicarboxylic acid and a tetracarboxylic dianhydride, a poly-proline-polyamine copolymer can be obtained. Here, the ratio of the organic dicarboxylic acid to the tetracarboxylic dianhydride may be within a range not impairing the effects of the present invention, and is preferably 10 mol% or less as a standard.

Further, the polyamidoquinone imine can be produced by chemically imidating the polyamine-polyamine copolymer.

<4. Liquid crystal alignment agent of the present invention>

The liquid crystal alignment agent of the present invention comprises the above alkenyl-substituted nadic acid ruthenium imide compound, the above heterocyclic compound, and the above-described poly-proline or derivative thereof. The liquid crystal alignment agent of the present invention may further contain a solvent, and may further contain various additives included in a general liquid crystal alignment agent, from the viewpoints of adjustment of physical properties such as viscosity, ease of availability, and simplification of steps.

The content of the alkenyl-substituted nadic acid ylide imide compound of the modifier in the liquid crystal alignment agent is preferably a total amount per 100 parts by weight of the poly-proline or a derivative thereof in the liquid crystal alignment agent. It is preferably from 1 to 100 parts by weight, more preferably from 1 to 70 parts by weight, still more preferably from 1 to 50 parts by weight, from the viewpoint of long-term stability of electrical characteristics when used as a liquid crystal display element.

The ratio of the aforementioned heterocyclic compound of the modifier in the liquid crystal alignment agent of the present invention is preferably 100 parts by weight of polyamic acid or the viewpoint of long-term stability of electrical properties when used as a liquid crystal display element. The derivative thereof is from 1 to 100 parts by weight, more preferably from 1 to 70 parts by weight, still more preferably from 1 to 50 parts by weight, based on the total amount.

The content of the aforementioned heterocyclic ring structure in the liquid crystal alignment agent in the above heterocyclic compound depends on the kind of the heterocyclic structure. The relationship between the decrease in the ion density and the increase in the chronological property of the liquid crystal display element and the aforementioned heterocyclic compound is not determined as described above, and it is generally considered that the amount of the heterocyclic structure is related to the performance of the above effect. .

The content of the oxirane compound in the liquid crystal alignment agent is preferably converted to ethylene oxide in terms of the ethylene oxide structure in the oxirane compound, and is preferably relative to polyglycine or a derivative thereof. 0.1 to 80% by weight. The content of the oxycyclobutane compound in the liquid crystal aligning agent is preferably converted to oxycyclobutane in terms of the oxycyclobutane structure in the oxocyclobutane compound, and is preferably relative to the polyaminic acid or its derivative. 0.1 to 80% by weight. Further, the content of the thiirane compound in the liquid crystal alignment agent is preferably 0.1 to 80 based on the polythiouric acid or its derivative when the thiopyran structure in the thiopyran compound is converted into a thiopyran. weight%. Further, the content of the aziridine compound in the liquid crystal alignment agent is preferably a polyacrylic acid or a derivative thereof when the aziridine structure in the aziridine compound is converted to aziridine. It is 0.1 to 80% by weight. Further, when the content of the oxazoline compound in the liquid crystal alignment agent is converted to an oxazoline structure in the oxazoline compound, it is preferably 0.1 to 0.1% of the poly-amic acid or the derivative thereof. 80% by weight. Further, the content of the oxazine compound in the liquid crystal alignment agent is preferably from 0.1 to 80% by weight based on the polyaminic acid or a derivative thereof when the oxazine structure in the oxazine compound is converted into an oxazine.

Further, when the heterocyclic compound contains two or more kinds of heterocyclic structures, the content of the heterocyclic ring structure in the liquid crystal alignment agent is determined from the ratio of each heterocyclic ring structure in the heterocyclic compound.

The ratio of the above heterocyclic compound to the alkenyl-substituted nadic acid ylide imide compound in the liquid crystal alignment agent is suppressed from the viewpoint of a decrease in ion density and a diachronic increase in ion density when the liquid crystal display element is formed. The weight ratio is preferably from 0.1 to 10, more preferably from 0.5 to 5.

As the polyaminic acid or a derivative thereof of the present invention, the aforementioned polyaminic acid or a derivative thereof can be used. For example, in the case of a poly-proline, a poly-proline which is obtained by reacting the A component or the B component of the acid with the A component or the B component of the amine, and the A component and the B component of the acid are mentioned. Polylysine obtained by reacting the component A or the component B of the amine, polyamine obtained by reacting the component A or component B of the acid with the component A and the component B of the amine, and the acid Polyamide or the like obtained by reacting the component A and the component B with the component A and the component B of the amine.

The content ratio of the poly-proline or a derivative thereof in the liquid crystal alignment agent of the present invention can be appropriately selected depending on the coating method in which the liquid crystal alignment agent is applied onto the substrate. For example, a printing machine used in a manufacturing process of a general liquid crystal display element (including an offset priter and an ink jet printer; hereinafter, simply referred to as "printer") is used in a liquid crystal alignment agent. The content of the acid or its derivative is preferably from 0.5 to 30% by weight, more preferably from 1 to 15% by weight, based on the total amount, and can be appropriately adjusted depending on the relationship with the viscosity of the liquid crystal alignment agent.

The solvent used in the present invention broadly includes a solvent which is usually used in a production step and a use of a polymer component such as polylysine, soluble polyimine, and polyamidoximine, and may be appropriately used depending on the intended use. select. The solvent is preferably (1) an aprotic polar organic solvent which is soluble in polylysine and a soluble polyimine, and (2) which is intended to improve coating properties by changing surface tension. A solvent mixture of solvents.

When these solvents are exemplified, they are as follows.

(1) An aprotic polar organic solvent (hereinafter, an aprotic polar organic solvent) having a polyacetic acid and a soluble polyimine as a good solvent, for example, N-methyl-2-pyrrolidone, Dimethylimidazolidinone, N-methyl caprolactam, N-methylpropionamide, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamidine Amine, N,N-diethylformamide, diethylacetamide, γ-butyrolactone, γ-valerolactone. Among these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, γ-valerolactone, and the like are more preferably exemplified.

(2) A solvent (hereinafter, another solvent) for the purpose of improving surface properties and improving coating properties, for example, alkyl lactate, 3-methyl-3-methoxyheptanol, tetrahydronaphthalene, or different Ethylene glycol monoalkyl ether such as phorone or ethylene glycol monobutyl ether; diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether; ethylene glycol monoalkyl ether or phenyl acetate; a propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether or propylene glycol monobutyl ether; dipropylene glycol monoalkyl ether such as dialkyl malonate or dipropylene glycol monomethyl ether; These ester compounds such as 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 type and ratio of the aprotic polar solvent and other solvents can be appropriately set in consideration of printability, coatability, solubility, and storage stability of the liquid crystal alignment agent. In contrast, the solubility and storage stability of the aprotic polar solvent are superior to those of other solvents, and other solvents tend to be excellent in printability and coating properties.

As described above, the liquid crystal alignment agent of the present invention may also contain various additives. As the various additives, a polymer compound other than polyamic acid or a derivative thereof or a low molecular compound can be selected and used depending on the purpose.

For example, a polymer compound which is soluble in an organic solvent is used as an additive, and by adding these additives, electrical characteristics and alignment properties of the formed liquid crystal alignment film can be controlled. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, and polyoxygen modified polyamine. Formate, polyoxymethylene modified polyester, and the like.

Further, as an additive of a low molecular compound, for example, (1) a surfactant may be used for a related purpose when it is desired to increase the coatability, and (2) an antistatic agent may be used when it is necessary to increase the antistatic property, (3) When it is desired to increase the adhesion to the substrate and the polishing resistance, a decane coupling agent and a titanium coupling agent can be used, and (4) when the oxime imidization is carried out at a low temperature, a ruthenium amide catalyst can be used. .

Examples of the above decane coupling agent include vinyltrimethoxydecane, vinyltriethoxydecane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxy. Decane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-amino group Phenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy Baseline, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylene) -3-(triethoxycarbenyl)-1-propylamine, N,N'-bis[3-(trimethoxymethylalkyl)propyl]ethylenediamine, and the like.

As an example of the ruthenium amide catalyst, it is preferred to add an aliphatic amine such as trimethylamine, triethylamine, tripropylamine or tributylamine; N,N-dimethylaniline, N,N-di Aromatic amines such as ethyl aniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substitution A catalyst such as an isoquinoline, a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole, or a cyclic amine such as a hydroxy-substituted imidazole. In particular, N,N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, isoquinoline and the like can be mentioned.

The amount of the decane coupling agent to be added is usually from 0 to 10% by weight, preferably from 0.1 to 3% by weight based on the total amount of the polyamidamine or its derivative.

The amount of the ruthenium-imiding catalyst to be added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, to the carbonyl group of the poly-proline or its derivative.

The amount of the other additives to be added varies depending on the use thereof, and is usually from 0 to 30% by weight, preferably from 0.1 to 10% by weight based on the total amount of the polyaminic acid or its derivative.

Another preferred embodiment of the liquid crystal alignment agent used in the present invention is a composition comprising two or more kinds of polyaminic acid.

For example, in the case of a liquid crystal alignment agent containing two kinds of polyaminic acid, a liquid crystal alignment agent containing a first polyamine and a second polyamic acid; and a tetracarboxylic acid in the first polyamine A compound having a side chain structure in one or two of an anhydride and a diamine, and a compound having a side chain structure in any one of tetracarboxylic dianhydride and diamine is not used in the second polyamic acid. More specifically, one of the poly-proline acids, one or two of the acid component A and the component B, and the polyamine derivative or its derivative I obtained by reacting the component A of the amine (hereinafter, also referred to as " Poly-proline acid I"), and the other is a poly-proline or a derivative thereof obtained by reacting one or both of the A component and the B component of the acid with the component B of the amine (hereinafter, also referred to as "poly" Amino acid II").

The composition of the polyaminic acid I of the present invention and the polyamic acid II is prepared by mixing the above polyamic acid I with polyamic acid II. The weight ratio of the mixed polyaminic acid I to the polyamic acid II is preferably I/II = 99/1 to 50/50, more preferably I/II = 95/5 to 80/20. The weight ratio can be appropriately adjusted according to the obtained pretilt angle, and if the ratio of the polyaminic acid II is increased, the pretilt angle can be increased.

Further, the liquid crystal alignment agent of the present invention may contain only polyamic acid I and II, and may further contain polyamic acid or a derivative thereof other than polyamic acid I and II.

As the diamine I-2, one or two or more kinds of diamines are used, and at least the diamines represented by the above formulas (II) to (VIII) are used. The polyamic acid I synthesized from the component A of the amine and the tetracarboxylic dianhydride can effectively impart a liquid crystal display element including a liquid crystal alignment film formed using the liquid crystal alignment agent containing the polyamic acid I. Good ion density.

Further, the diamine I-2 may be used in combination with any other diamine as needed. Here, examples of the other diamines include diamines represented by the above formulas (VIII) to (XII) and (X V), oxime diamines, and decane diamines.

The molar ratio of the component A of the amine in the diamine in the polyamic acid I can be determined according to the structure of the selected diamine represented by the above formula (I) to (VII), and desired. The ion density and long-term reliability are adjusted, and the total amount is preferably from 1 to 100%, more preferably from 5 to 80%.

On the other hand, the polyamic acid II can effectively impart a suitable pretilt angle to a liquid crystal display element including a liquid crystal alignment film formed using a liquid crystal alignment agent containing the polyphthalic acid II.

The component B of the above-mentioned amine in the diamine of the polyamic acid II is typically one or two or more kinds of diamines represented by the formulae (VIII) to (XII), but as a diamine which can be used in combination. Examples of the diamine, fluorene-based diamine, and decane-based diamine represented by the above formulas (I) to (VII).

By combining (mixing) the above polyamic acid I with polyamic acid II, it is possible to impart preferred characteristics as the liquid crystal alignment agent of the present invention.

Specifically, the diamine which is a raw material of polylysine can impart a better ion density to the liquid crystal alignment film formed by using the composition of the present invention by appropriately selecting the kind and combination of the diamine used. And a suitable pretilt angle.

<5. Liquid crystal alignment film of the present invention>

The liquid crystal alignment film of the present invention is a liquid crystal alignment film formed by calcining the polyamic acid and the modifier in the liquid crystal alignment agent of the present invention in a film form.

In the liquid crystal alignment film, for example, the liquid crystal alignment agent of the present invention can be applied to a substrate for liquid crystal display element or a substrate for measurement such as calcium fluoride or polyfluorene oxide, and the film of the liquid crystal alignment agent can be heated to, for example, 150~. It is formed at 400 ° C, preferably 180 to 280 ° C. The film thickness of the liquid crystal alignment film here is preferably from 10 to 300 nm, more preferably from 30 to 100 nm. Further, it is preferred to subject the liquid crystal alignment film to a polishing treatment.

The film thickness of the liquid crystal alignment film can be adjusted according to the viscosity of the liquid crystal alignment agent and the method of applying the liquid crystal alignment agent. Further, the film thickness of the liquid crystal alignment film can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Further, the components in the liquid crystal alignment film are subjected to hydrolysis or the like as necessary, and can be analyzed by a usual analysis method such as IR or MS.

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

The liquid crystal display device of the present invention comprises: (1) a pair of substrates disposed opposite to each other, (2) a liquid crystal alignment film of the present invention formed on each of the pair of substrates, and (3) sandwiched between a liquid crystal layer between the pair of substrates.

The pair of electrode-attached substrates arranged in the opposite direction are preferably a transparent substrate (for example, a glass substrate).

Electrodes are provided on the surface of at least one or both of the pair of substrates in accordance with the form 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. Examples of such an electrode include a vapor deposition film of ITO and metal. The electrodes may be formed on the entire surface of the substrate, for example, may be patterned to form a specific shape. On the substrate provided with the electrode, the liquid crystal alignment film of the present invention is formed on the surface of the substrate, and the liquid crystal alignment film of the present invention is formed on the electrode on the substrate on which the electrode is provided. The formation of the liquid crystal alignment film of the present invention is as described above.

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

An example of a preferred liquid crystal composition having a positive dielectric anisotropy is disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open No. Hei 8- Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), Japanese Patent Laid-Open No. Hei 10-204016 (EP844229A1), Japan Japanese Laid-Open Patent Publication No. Hei 10-204436, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. No. Hei.

The liquid crystal composition used in the VA liquid crystal display device can be made into various liquid crystal compositions having a negative dielectric anisotropy. Examples of a preferred liquid crystal composition are disclosed in Japanese Laid-Open Patent Publication No. SHO 57-114532, Japanese Patent Laid-Open No. Hei No. 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, and Japanese Patent Laid-Open No. Hei 8-40953 Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei 10- No. Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Application Laid-Open No. Hei No. Hei 10--237000, Japanese Patent Laid-Open No. Hei 10-237004 Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Laid-Open No. Hei 10-237076, and Japanese Patent Laid-Open No. Hei 10-237448 Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10-- Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 072626, Japanese Patent Laid-Open No. 2001-192657, and the like.

It is also possible to use one or more optically active compounds in the liquid crystal composition having positive or negative dielectric anisotropy.

The liquid crystal display element of the present invention may of course have other components.

For example, in a TFT-type liquid crystal device 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 may be blocked on the second transparent substrate. A black matrix of light other than the pixel area, a color filter, a planarization film, a pixel electrode, and the like.

Further, in the VA liquid crystal display device, in particular, the MVA liquid crystal display device, minute projections called domains are formed on the first transparent substrate. Further, a panel gap adjusting spacer between the substrates may be formed.

The liquid crystal display element of the present invention can be produced by any method, for example, by a method comprising the steps of: (1) coating a liquid crystal alignment agent on the two transparent substrates, and (2) coating the coating. a step of drying the liquid crystal alignment agent, (3) performing a heat treatment step of dehydrating and ring-closing the dried liquid crystal alignment agent, and (4) performing a step of aligning the obtained alignment film, (5) After the two substrates have a specific gap and are bonded together, the liquid crystal is sealed in the gap between the substrates, or the liquid crystal is dropped on one of the substrates and then bonded to the other substrate.

As a coating method in the step of applying the liquid crystal alignment agent, a rotator method, a printing method, a dipping method, a dropping method, an inkjet method, or the like is generally known. These methods are also applicable to the present invention.

In addition, as a method of performing the heat treatment step necessary for the drying step and the dehydration reaction, generally, a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, etc. . These methods are also applicable to the present invention. The drying step is preferably carried out at a relatively low temperature (50 to 140 ° C) in a range in which the solvent can evaporate. The heat treatment step is generally carried out at a temperature of about 150 to 300 °C.

In the alignment treatment of the liquid crystal alignment film, in the IPS type liquid crystal display element, the OCB type liquid crystal display element, the TN type liquid crystal display element, and the STN type liquid crystal display element, polishing processing is usually performed. In the VA type liquid crystal display element, the polishing treatment is often not performed.

Next, the adhesive is applied and bonded to one of the substrates, and the liquid crystal is injected into the vacuum. In the case of the dropwise addition method, the liquid crystal is dropped on the substrate before bonding, and thereafter bonded to the other substrate. The liquid crystal display element of the present invention is produced by hardening an adhesive used for bonding by heat or ultraviolet rays.

A polarizing plate (polarizing film), a wavelength plate, a light-scattering film, a driving circuit, and the like may be attached to the liquid crystal display element of the present invention.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. Further, the names of the tetracarboxylic dianhydride, the diamine, the alkenyl group substituted with the nadic acid sulfonium imide compound, the heterocyclic compound, and the solvent used in the examples are indicated by the following ellipsis.

[tetracarboxylic dianhydride] pyromellitic dianhydride {structural formula (1)}: PMDA 1,2,3,4-cyclobutane tetracarboxylic dianhydride {structural formula (19)}: CBDA

[Diamine] 4,4'-diaminodiphenylmethane {structural formula (V-1)}: DDM 4,4-[1,3-propane bis(4,1-phenylphenylmethylene) ] bis [aniline] {structural formula (VII-2)}: BABZP3 2-(phenylmethyl)-1,4-diaminobenzene {structural formula (IV-16)}: PhPDA 5-[[4- (4'-pentyl[1,1'-dicyclohexyl]-4-yl)phenyl]methyl]-1,3-diaminobenzene {Formula (VIII-5)/R ²³ =C ₅ H ₁₁ }: 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-n-hexylcyclohexyl)cyclohexane {Formula (XI-4)/R ³⁰ =C5H ₁₁ }: 5ChChBA 4,4'-vinyldiphenylamine {structural formula (V-7)}: DET [alkenyl-substituted nadic acid ylidene imine compound] is a compound represented by the following structural formula (I na-1) :BANI-M

[化52]

[Ethylene oxide compound] 4,4'-methylenebis(N,N-diglycidylaniline): DGA(3-glycidoxypropyl)trimethoxydecane: TMS (3-glycidol) Oxypropyl)methyldimethoxydecane: DMS2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane: ECS

[oxetane compound] bis[(3-ethyl-3-epoxypropenylmethoxy)methyl]benzene: BMMB

[aziridine compound] 2,4,6-tris(1'-aziridine)-1,3,5-triazine: ATA

[thiirane compound] N, N, N', N'-tetrathiopyranylmethyl-4,4'-diaminodiphenylmethane: TMAP

[oxazoline compound] poly(styrene-co-2-isopropenyloxazoline) (manufactured by Nippon Shokubai Co., Ltd.: EPOCROS RPS-1005): PSO

[oxazin compound] bis(3-phenyl-3,4-dihydro-2H-1,3-phenyloxazin-6-yl)methane (F-a type of benzoxazine produced by Shikoku Chemical Industries Co., Ltd.) :BOZ

[Solvent] N-methyl-2-pyrrolidone: NMP butyl cellulolytic (ethylene glycol monobutyl ether): BC

<1. Synthesis of polyaminic acid> [Synthesis of polyglycine]

Synthesis Example 1 In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 1.6760 g of 5ChCh, 1.7918 g of PhPDA, and 58.3 g of dehydrated NMP were placed in a dry nitrogen stream. Stir and dissolve. Next, 2.5321 g of CBDA was added and reacted at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 70 ° C or lower to carry out the reaction. To the resulting solution, 37.7 g of BC was added to synthesize a polyglycine solution (PA1) having a concentration of 6% by weight. The obtained PA1 had a weight average molecular weight of 37,000.

Here, the obtained polylysine was diluted to a polyglycine concentration of about 1% by weight with a diluent composed of phosphoric acid and DMF (phosphoric acid/DMF=0.6/100:weight ratio), using Chromatopac C-R7A ( The product was prepared by the Shimadzu Corporation, and the weight average molecular weight of the polyaminic acid was determined by a GPC method and converted to polystyrene. In addition, the column was measured using a GF-7HQ (manufactured by Showa Denko Co., Ltd.) under the conditions of a column temperature of 50 ° C and a flow rate of 0.6 mL/min.

In the synthesis examples 2 to 6, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1, the polyaminic acid solution (PA2 to PA6) was synthesized in accordance with Synthesis Example 1. The results including Synthesis Example 1 are collectively shown in Table 1.

[Table 1]

<2. Production of liquid crystal display element> [Example 1]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine solution (PA2) synthesized in Synthesis Example 2 were mixed at a weight ratio of 1/9. In the obtained mixture, 10 parts by weight of BANI-M as an alkenyl-substituted nadic acid ruthenium imide compound, and DGA as an oxirane compound are added per 100 parts by weight of polyglycine, and improvements including these compounds are included. The total amount of the agent was adjusted to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element as described below was produced.

In the method of producing a liquid crystal display device, a liquid crystal alignment agent was applied onto a glass substrate with two ITO electrodes by a spinner to form a film having a film thickness of 70 nm. After coating, the film was dried by heating at 80 ° C for about 5 minutes, followed by heat treatment at 220 ° C for 40 minutes, followed by a grinding treatment to form a liquid crystal alignment film.

The liquid crystal alignment film formed on the glass substrate was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, followed by drying in an oven at 120 ° C for 30 minutes.

4 μm of the spacer is spread on one glass substrate, and the surface on which the liquid crystal alignment film is formed is set as the inner side, and the pair of glass substrates forming the liquid crystal alignment film are opposed to each other so that the polishing direction is parallel in the opposite direction, followed by epoxy The hardener seals the periphery of the liquid crystal alignment film to form an anti-parallel cell having an interval of 4 μm. In this unit, the liquid crystal composition I shown below was injected into the space, and the liquid crystal composition was sealed with an injection port with a light hardener. Next, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element.

Liquid crystal composition I

[Embodiment 2]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine 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 as an alkenyl-substituted dysinoid compound and BOZ as an oxazine compound are added per 100 parts by weight of the poly-proline, and a modifier containing these compounds is added. The total amount was set to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 3]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the resulting mixture, 10 parts by weight of BANI-M as an alkenyl-substituted nadic acid ruthenium imide compound and BMMB as an oxetane compound are added per 100 parts by weight of polyglycine, and these will be contained. The total amount of the modifier of the compound was set to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 4]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine 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 as an alkenyl-substituted nadic acid ruthenium imide compound, and ATA as an aziridine compound are added per 100 parts by weight of the poly-proline, and a modifier containing these compounds is added. The total amount was set to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 5]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine 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 as an alkenyl-substituted nadic acid ruthenium imide compound, and TMAP as a thiopyran compound are added per 100 parts by weight of the poly-proline, and a modifier containing these compounds is added. The total amount was set to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 6]

A 6% by weight poly-proline solution (PA1) synthesized in Synthesis Example 1 and a 6% by weight poly-proline 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 as an alkenyl-substituted nadic acid ruthenium imide compound, and PSO as an oxazoline compound are added per 100 parts by weight of polyglycine, and a modifier containing these compounds is added. The total amount was set to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 7]

A 5% by weight poly-proline solution (PA1) synthesized in Synthesis Example 1 and a 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the resulting mixture, 30 parts by weight of BANI-M as an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of poly-proline, and 10 parts by weight per 100 parts by weight of polyglycine as an oxazine compound In BOZ, the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 1]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine solution (PA2) synthesized in Synthesis Example 2 were mixed at a weight ratio of 1/9. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 2]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 3]

A 6% by weight poly-proline solution (PA1) synthesized in Synthesis Example 1 and a 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the resulting mixture, 10 parts by weight of BANI-M as an alkenyl-substituted nadic acid ruthenium imide compound was added per 100 parts by weight of polyamine. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 4]

The 6% by weight polylysine solution (PA1) synthesized in Synthesis Example 1 and the 6% by weight polylysine solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the resulting mixture, 10 parts by weight of PSO as an oxazoline was added per 100 parts by weight of polyamic acid. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 8]

In a 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3, 10 parts by weight of BANI-M as an alkenyl-substituted nadic acid ylide compound was added per 100 parts by weight of polyglycine. And the DGA which is an oxirane compound, the total amount of the modifier containing these compounds is 20 weight part. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and liquid crystal composition II shown below was used.

[Embodiment 9]

In the 6% by weight poly-proline solution (PA2) synthesized in Synthesis Example 2, 10 parts by weight of BANI-M as an alkenyl-substituted nadic acid ylide compound was added per 100 parts by weight of polyglycine. And the BOZ which is an oxazine compound, the total amount of the modifier containing these compounds is 20 weight part. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and liquid crystal composition II was used.

[Comparative Example 5]

To a 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3, 20 parts by weight of BANI-M as an alkenyl-substituted nadic acid ruthenium imide compound was added per 100 parts by weight of polyglycolic acid. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and liquid crystal composition II was used.

[Embodiment 10]

A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline 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 as an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of polylysine, and 20 parts by weight per 100 parts by weight of polyglycine as epoxy B The TMS of the alkane compound, the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 11]

A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline 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 as an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of polylysine, and 20 parts by weight per 100 parts by weight of polyglycine as epoxy B The DMS of the oxirane compound was set to 40 parts by weight based on the total amount of the modifier containing these compounds. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 12]

A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline 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 as an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of polylysine, and 20 parts by weight per 100 parts by weight of polyglycine as epoxy B The ECS of the oxirane compound was set to 40 parts by weight based on the total amount of the modifier containing these compounds. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 13]

The 6% by weight polylysine solution (PA4) synthesized in Synthesis Example 4 and the 6% by weight polylysine 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 as an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of polylysine, and 20 parts by weight per 100 parts by weight of polyglycine as epoxy B The TMS of the oxirane compound was set to 40 parts by weight based on the total amount of the modifier containing these compounds. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 14]

The 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and the 6% by weight poly-proline 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 as an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of polylysine, and 20 parts by weight per 100 parts by weight of polyglycine as epoxy B The ECS of the oxirane compound was set to 40 parts by weight based on the total amount of the modifier containing these compounds. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 6]

A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the resulting mixture, 20 parts by weight of BANI-M as an alkenyl-substituted nadic acid ruthenium imide compound was added per 100 parts by weight of polyamic acid. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 7]

A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. To the resulting mixture, 20 parts by weight of ECS as an oxirane compound was added per 100 parts by weight of polyamic acid. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 8]

A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were mixed at a weight ratio of 8/2. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

<3. Evaluation of electrical characteristics> [Test Examples 1 to 22]

The liquid crystal display elements produced in Examples 1 to 14 and Comparative Examples 1 to 8 were measured for ion density and long-term reliability of electrical characteristics as follows.

(1) Measurement of ion density The ion density was measured using a liquid crystal physical property evaluation device 6254 manufactured by TOYO Technica. The measurement conditions were: waveform: triangular wave, frequency: 0.01 Hz, voltage: ±10 V, and measurement temperature was 60 °C. The smaller the ion density 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] The ion density [pC] was determined for the liquid crystal display element produced, and the retention characteristics were evaluated. The test method for maintaining the characteristics was a method in which the liquid crystal display element was allowed to stand in an environment at a temperature of 60 ° C for 100 hours, and the extracted ion density [pC] was measured over the course of time. The smaller the decrease in the ion density (for example, the increase rate is less than 1.5 times: the increase rate (time) = the ion density after 100 hours / the ion density at the initial stage (0 hour)) the better the retention characteristics of the ion density, and the long-term electrical characteristics. The better the reliability. The results are shown in Table 2.

(2-2) Measurement of retention characteristics of ion density [Test Examples 15 to 22] The ion density [pC] was determined for the liquid crystal display element produced, and the retention characteristics were evaluated. In the test method for maintaining characteristics, the liquid crystal display element was placed in an environment at a temperature of 100 ° C for 100 hours, and the extracted ion density [pC] was measured over the course of time. The smaller the decrease in ion density (for example, the increase rate is less than 5.0 times: the increase rate (time) = the ion density after 100 hours / the ion density of the initial (0 hour)), the better the retention characteristics of the ion density, and the long-term electrical characteristics. The better the reliability. The results are shown in Table 3.

As shown in Table 2 and Table 3, when a liquid crystal display element in which a liquid crystal alignment film of the above-described modifier is mixed is used, a decrease in ion density retention characteristics is remarkably suppressed.

As described above, the liquid crystal alignment agent containing the polyamic acid and the above-described improver of the present invention has a high ion density when the liquid crystal alignment film of the liquid crystal display element is formed, and the retention property can be remarkably suppressed.

Claims (20)

A liquid crystal alignment agent, wherein the liquid crystal alignment agent is a liquid crystal alignment agent comprising polylysine or a derivative thereof, an alkenyl-substituted nadimide compound, and a heterocyclic compound, characterized in that the heterocyclic ring The compound has a heterocyclic ring structure selected from one or more of the group consisting of ethylene oxide, oxocyclobutane, thiopyran, aziridine, oxazoline, and oxazine. The liquid crystal alignment agent according to claim 1, wherein the alkenyl-substituted nadic acid ylide compound is a compound represented by the following formula (I na). In the formula (I na), R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or benzyl group. The group n represents an integer of 1 to 2, and when n=1, R ³ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a benzyl group. -(C _q H _2q )-O _t -(C _r H _2r O) _u -C _s H _2s+1 (q, r, s represent an integer of 2~6, t represents 0 or 1, u represents 1~30 The integer poly) alkylene alkyl group represented by -(R) _v -C ₆ H ₄ -R ⁴ (v represents 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a group represented by hydrogen or an alkyl group having 1 to 4 carbon atoms, and -C ₆ H ₄ -T-C ₆ H ₅ (T represents -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, a group represented by -S- or -SO ₂ -) or a group in which one or three hydrogens directly bonded to the aromatic ring are substituted with a hydroxyl group, and when n=2, R ³ represents a carbon number of 2 to 20 The alkyl group, the cycloalkyl group having a carbon number of 5-8, and -(C _q H _2q O) _t -(C _r H _2r O) _u -C _s H _2s -(q, r, s respectively represent 2 An integer of ~6, t represents 0 or 1, and u represents an integer of 1 to 30), and the number of carbon atoms is 6~ An extended aryl group of 12, with -(R) _v -C ₆ H ₄ -R ⁵ - (v represents 0 or 1, and R and R ⁵ each represent an alkylene group having a carbon number of 1 to 4 or a carbon number of 5 to 8; The group represented by cycloalkyl), -C ₆ H ₄ -T-C ₆ H ₄ - (T represents -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, - a group represented by OC 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 A group substituted by a hydroxyl group. The liquid crystal alignment agent according to claim 2, wherein the alkenyl-substituted nadic acid ylidene imide compound is represented by the following structural formula (I na-1) to (I na-3); One or two or more compounds, [Chemical 2] . The liquid crystal alignment agent according to claim 1, which comprises the above alkenyl substitution in an amount of from 1 to 100 parts by weight based on 100 parts by weight (based on the total amount) of the polyamic acid or derivative thereof Nadick acid ylide compound. The liquid crystal alignment agent according to claim 1, wherein the heterocyclic compound comprises a compound having two or more of the aforementioned heterocyclic structures, and comprises 100 parts by weight of the aforementioned polyaminic acid or a derivative thereof ( The total amount is 1 to 100 parts by weight of the aforementioned compound. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid or a derivative thereof is obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. Proline. The liquid crystal alignment agent according to claim 6, wherein the acid component comprises an A component and a B component, and the acid component A comprises an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride is a compound selected from one or more of the group consisting of the following structural formulae (1), (2), (5) to (7), and (14), . The liquid crystal alignment agent according to claim 7, wherein the aromatic tetracarboxylic dianhydride is a compound of the above structural formula (1). The liquid crystal alignment agent according to claim 7, wherein the B component of the acid contains either or both of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 9, wherein the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are selected from the following structural formulas (19) and (23). One or more compounds of the group consisting of (25), (35)~(37), (39), (44), and (49), [Chemical 4] . The liquid crystal alignment agent according to claim 10, wherein the alicyclic tetracarboxylic dianhydride is a compound of the above structural formula (19). The liquid crystal alignment agent according to claim 6, wherein the amine component separately contains the A component or the two components of the A component and the B component, and the A component of the amine is selected from the following formula ( a compound represented by one or more formulas of the group consisting of I)~(VII), [Chemical 5]H ₂ N-A ¹ -NH ₂ (I) In the formula (I), A ¹ represents -(CH ₂ ) _m -, wherein m represents an integer of 1 to 12, and in the formulae (III), (V) and (VII), A ¹ independently represents a single bond. , -O-, -S-, -S-S-, -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-, where m independently represents an integer from 1 to 12, and the formula (VI) Wherein A ₂ independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having 1 to 6 carbon atoms; The hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulae (II) to (VII) may be independently substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, - PO ₃ H ₂ , benzyl or 4-hydroxybenzyl. The liquid crystal alignment agent according to claim 12, wherein the component A of the amine is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV) -16), one or more compounds of the group consisting of (V-1)~(V-12), (V-33) and (VII-2), . The liquid crystal alignment agent according to claim 12, wherein the component B of the amine is one or more of a group selected from the group consisting of the following general formulae (VIII) to (XII) Compound represented, [Chem. 7] In the formula (VIII), R ¹ represents 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, and R ² represents a group having a steroid skeleton, a group represented by the following formula (XIII), an alkyl group having 1 to 30 carbon atoms, or a phenyl group, in the above-mentioned alkylene When the carbon number of the group and the alkyl group is 2 or more, any -CH ₂ - may be independently substituted by -O-, -CH=CH- or -C≡C- (wherein the oxygen is discontinuous), the aforementioned phenyl group The hydrogen may also be independently substituted by fluorine, methyl, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy, except that -R ¹ -R ² represents a benzyl group. In the formula (IX), R ³ independently represents hydrogen or a methyl group, R ⁴ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ⁵ independently represents a single bond, -CO- or -CH ₂ -, and In X), R ³ independently represents hydrogen or a methyl group, R ⁴ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ⁵ independently represents a single bond, -CO- or -CH ₂ -, R ⁶ and R ⁷ Each independently represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group, and in the formula (XI), R ⁸ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - in the alkyl group having 2 or more carbon atoms may be independently substituted by -O-, -CH=CH- or -C≡C- ( Wherein the oxygen is discontinuous, R ⁹ independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and ring A represents a 1,4-phenylene group or a 1,4-cyclohexyl group, and a represents 0 or 1, b represents 0, 1 or 2, and c independently represents 0 or 1. In the formula (XII), R1 ⁰ represents an alkyl group having 3 to 30 carbon atoms, or a fluorinated alkyl group having 3 to 30 carbon atoms, R ¹¹ Represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group having 1 to 30 carbon atoms, and R ¹² independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and d independently represents 0 or 1, In the formula ( ^XIII ), R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and carbon. An alkylene group having 1 to 3 alkyl groups (in which oxygen is discontinuous) or a stretching alkyl group having 1 to 3 carbon atoms (wherein oxygen is discontinuous), and R ¹⁶ and R ¹⁷ each independently represent hydrogen, fluorine or methyl group. R ¹⁸ represents hydrogen, fluorine, chlorine, cyano, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a monofluoromethyl group, and 2 a fluoromethyl group, a trifluoromethyl group, a monofluoromethoxy group, a difluoromethoxy group or a trifluoromethoxy group, any of the above alkyl group having 2 or more carbon atoms, the alkoxy group and the alkoxyalkyl group described above -CH ₂ - may also be substituted by a difluoromethylene group or a group represented by the following formula (X IV), and ring B and ring C each independently represent a 1,4-phenylene group or a 1,4-ring group. Each of f, g, and h independently represents an integer of 0 to 4, i, j, and k each independently represent an integer of 0 to 3, and the sum of these values is 1 or more, and l and m respectively represent 1 Or 2, In the formula (X IV), R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 1 to 100. The liquid crystal alignment agent according to claim 14, wherein the component B of the amine is selected from the group consisting of the following general formulae (VIII-2), (VIII-4), (VIII-5), a compound represented by one or more formulas of the group consisting of VIII-6), (XI-2) and (XI-4), In the above formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or carbon number. 1 to 20 alkyl groups. The liquid crystal alignment agent according to any one of claims 1 to 15, which comprises two or more of the above polylysine or a derivative thereof. A liquid crystal alignment agent, wherein the liquid crystal alignment agent is a liquid crystal alignment agent comprising polylysine or a derivative thereof, an alkenyl-substituted nadic acid ruthenium imine compound, and a heterocyclic compound, wherein the poly-lysine or a derivative thereof The polyamic acid obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component, wherein the acid component contains the component A and the component B, and the component A of the acid is selected from the following structural formula ( One or two or more compounds of the group consisting of 1), (2), (5) to (7), and (14), wherein the B component of the acid is selected from the following structural formulae (19), (23) One or two or more compounds of the group consisting of (25), (35) to (37), (39), (44), and (49), wherein the amine component alone contains the component A or contains the component A. And the two components of the B component, the A component of the amine is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V) -12), one or two or more compounds of the group consisting of (V-33) and (VII-2), wherein the component B of the amine is selected from the following formulas (VIII-2) and (VIII-4) ), (VIII-5), (VIII-6), (XI-2) and a compound represented by one or more formulas of the group consisting of XI-4), the alkenyl-substituted nadic acid ylidene imide compound, comprising the following structural formula (I na-1)~(I na-3 One or more of the compounds represented by the above heterocyclic compound having one selected from the group consisting of ethylene oxide, oxycyclobutane, thiopyran, aziridine, oxazoline, and oxazine Or more than two heterocyclic structures, [Chem. 11] [Chemistry 13] [Chemistry 14] In the above formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or carbon number. 1~20 alkyl, [15] . The liquid crystal alignment agent according to claim 17, wherein the A component of the acid is a compound represented by the structural formula (1), and the B component of the acid is the structural formula (19). The compound represented by the above-mentioned amine is one or two or more compounds represented by the above structural formulas (IV-16), (V-1), (V-7) and (VII-2), and the aforementioned amine The component B is one or two or more compounds represented by the above formulas (VIII-5), (XI-2) and (XI-4), and the alkenyl-substituted nadic acid ruthenium imide compound is a compound represented by the above formula (I na-1), wherein the heterocyclic compound comprises 4,4'-methylenebis(N,N-diglycidylaniline) or (3-glycidoxypropyl) Trimethoxydecane, (3-glycidylpropyl)methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, bis[(3-ethyl-) 3-epoxypropenylmethoxy)methyl]benzene, 2,4,6-tris(1'-aziridine)-1,3,5-triazine, N,N,N',N' -tetrathiopyranylmethyl-4,4'-diaminodiphenylmethane, poly(styrene-co One or two of the group consisting of 2-isopropenyloxazoline) and bis(3-phenyl-3,4-dihydro-2H-1,3-phenyloxazin-6-yl)methane The above compounds. A liquid crystal alignment film obtained by calcining a liquid crystal alignment agent according to any one of claims 1 to 18 in a film state. A liquid crystal display device comprising: an opposite electrode disposed on a substrate and an electrode formed on one or both of opposite surfaces of the pair of substrates; and an opposite surface of each of the pair of substrates The liquid crystal display element of the liquid crystal alignment film and the liquid crystal display layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to claim 19.