TWI384029B - 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 which is a compound in which an alkenyl-substituted nadiimide compound and a radical polymerizable unsaturated double bond are combined in a polyamic acid.

The liquid crystal display element is used for a viewfinder, a projection display, or the like of a video camera represented by a monitor of a notebook personal computer or a desktop personal computer. Various liquid crystal display devices have recently been used as televisions. Further, the liquid crystal display element is also used as an optoelectronic related element such as an optical printer head, an optical Fourier transform device, or a light valve.

The liquid crystal display device usually has: 1) a pair of substrates arranged in the opposite direction, 2) electrodes formed on one or both of the opposing faces of the pair of substrates, and 3) respective ones of the pair of substrates a liquid crystal alignment film formed on the opposite surface, and 4) a liquid crystal layer formed between the pair of substrates.

The mainstream of the existing liquid crystal display elements is a display element using a nematic liquid crystal, which has been 1) twisted by 90 degrees. Twisted Nematic (TN) type liquid crystal display element, 2) Super Twisted Nematic (STN) type liquid crystal display element which is usually twisted by 180 degrees or more, 3) so-called thin film transistor A Thin Film Transistor (TFT) type liquid crystal display element is put into practical use. These liquid crystal display elements have a drawback in that the angle of view of the image can be appropriately seen, and when viewed from the oblique direction, a decrease in brightness or contrast and a brightness inversion in halftone are generated.

In recent years, the above-mentioned viewing angle problems have been improved by the following techniques: 1) a TN-TFT type liquid crystal display element using an optical compensation film, 2) a vertical alignment (VA) type liquid crystal display element using a vertical alignment and an optical compensation film. 3) Multi-domain Vertical Alignment (MVA) type liquid crystal display elements using vertical alignment and protruding structure technology, or 4) In-Plane Switching (IPS) type liquid crystal display Element, 5) Electrostatically Controlled Birefringence (ECB) type liquid crystal display element, 6) Optically Compensated Bend or Optically Self-Compensated Birefringence (OCB) type liquid crystal display element. Moreover, the improved technology is put into practical use, or research is being carried out to put these technologies into practical use.

The technical development of the liquid crystal display element is realized not only by improving these driving methods or element structures, but also by modifying the constituent members used for the liquid crystal display element. Among the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment film is an important element related to the display quality of the liquid crystal display element, and the liquid crystal alignment film The role of the liquid crystal display element has become important year by year.

The liquid crystal alignment film is prepared from a liquid crystal alignment agent. Currently, a liquid crystal alignment agent mainly used is a solution in which polylysine or a soluble polyimide is dissolved in an organic solvent. After such a solution is applied onto a substrate, a film is formed by heating or the like to form a polyimide film. Various liquid crystal alignment agents other than polyglycolic acid have also been studied, but from the viewpoints of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, and display properties, Most of them can't be put into practical use.

In order to improve the display quality of the liquid crystal display element, important characteristics required for the liquid crystal alignment film include ion density. If the ion density is high, sometimes the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered to hinder the normal gradation display. Further, even if the initial ion density is low, the ion density (long-term reliability) after the high-temperature acceleration test becomes high, which is a problem. On the other hand, if the residual charge is large, even if the voltage (OFF) is turned off after the voltage is applied, a so-called "after-image", that is, an image residue that should disappear, is generated. A decrease in long-term reliability or generation of an afterimage causes a deterioration in the display quality of the liquid crystal, which is a problem.

Recently, some methods have been proposed to try to solve the long-term reliability problem described.

1) A polyglycine composition for forming a liquid crystal alignment film and combining two or more kinds of polyaminic acid having different physical properties (for example, Japanese Patent Laid-Open No. Hei 11-193345 Japanese Patent Laid-Open No. 11-193347).

2) A varnish composition containing a polymer component containing polyphthalic acid and polyamine and a solvent (for example, International Publication No. 00/61684 pamphlet) is known.

3) A varnish composition containing two or more kinds of polyaminic acid having different physical properties, and polyamine and a solvent (for example, International Publication 01/000733 pamphlet) is known.

4) A varnish composition containing a polymer material containing a polyamine acid or the like synthesized using a diamine compound having a specific structure (for example, Japanese Patent Laid-Open Publication No. 2002-162630) is known. Bulletin).

5) A technique of adding a low molecular weight epoxy resin to a polyimide and a polyamid varnish is known (for example, Japanese Patent Laid-Open Publication No. Hei No. 2005-189270).

Further, some techniques for solving the problem of improving the performance of liquid crystal display elements by adding an additive to polyamic acid have been proposed. Such a technique, for example, a liquid crystal alignment agent containing a poly-proline and a hardening accelerator having a pyridine structure or a quinoline structure (for example, Japanese Patent Laid-Open Publication No. Hei 9-302225), A liquid crystal alignment agent containing a polyamic acid and an alkenyl group substituted with a nadic ylidene compound (for example, Japanese Patent Laid-Open No. 2004-341030 and Japanese Patent Laid-Open No. Hei 9-269491), and a poly-proline And a liquid crystal aligning agent of the epoxy group-containing compound (for example, Japanese Patent Laid-Open No. Hei 7-234410 and Japanese Patent Laid-Open Publication No. 2002-323701).

However, the use of these prior art techniques does not adequately address ion density and Long-term reliability issues. For example, in the Japanese Patent Publication No. Hei 9-302225, the curing accelerator evaporates, sublimes, and decomposes during the hydrazine imidization process in the production of a liquid crystal alignment film, and liquid crystals produced by using the liquid crystal alignment agent. In the alignment film, the influence of the hardening accelerator on the electrical characteristics of the liquid crystal alignment film has not been studied.

Further, for example, in Japanese Laid-Open Patent Publication No. 2002-323701, the adsorption of ionic impurities is included in the problem, and the voltage holding ratio of the produced liquid crystal display element is described in the examples. However, although the voltage holding ratio and the ion density are sometimes related, the initial voltage holding ratio may not be correlated with the ion density with time. This is considered to be because the ionic impurities are not only included in the element when the liquid crystal display element is produced, but also generated by, for example, liquid crystal decomposition accompanying the operation of the liquid crystal display element, and vary with time. Therefore, the technique of the Japanese Patent Publication No. 2002-323701, which is an ionic impurity, is considered to be a technique for effectively reducing the ionic impurities contained in the element when the liquid crystal display element is produced, but suppressing the ionic impurities. In terms of time generation, there is still room for research.

Recently, some methods have been proposed to try to solve the "after-image" problem described.

1) A polyglycine composition for forming a liquid crystal alignment film and combining two or more kinds of polyaminic acid having different physical properties (Japanese Patent Laid-Open No. Hei 11-193345 and Japanese Patent) Japanese Patent Laid-Open No. Hei 11-193347).

2) A varnish composition containing a polymer component containing a poly-proline and a polyamine and a solvent (International Publication No. 00/61684 pamphlet) is known.

3) A varnish composition containing two or more kinds of polyaminic acid having different physical properties, and polyamine and a solvent are known. (International Publication 01/000733 brochure).

4) A varnish composition containing a polymer material containing a polyamine acid or the like synthesized using a diamine compound having a specific structure (Japanese Patent Laid-Open Publication No. 2002-162630).

However, the "after-image" problem caused by the large residual charge cannot be sufficiently solved by using these prior art techniques.

In view of the above circumstances, it has been desired to develop a liquid crystal alignment agent for a liquid crystal display element having an ion density and a long-term reliability problem corresponding to an electrical characteristic accompanying a change in ion density with time variation, and using the liquid crystal display element. A liquid crystal alignment film formed by a liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

The present inventors conducted intensive studies in order to solve the above problems. As a result, it has been found that when a liquid crystal alignment agent obtained by combining an alkenyl group substituted with a nadic ylidene compound and a compound having a radical polymerizable unsaturated double bond as a modifier and polylysine is used, it can be produced. The liquid crystal display element of the liquid crystal alignment film imparts good ion density and long-term reliability, and has improved afterimage characteristics, thereby completing the present invention.

The liquid crystal alignment agent of the present invention is as shown in the following item [1].

[1] A liquid crystal alignment agent which is a composition containing an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and a polyglycine or a derivative thereof, and an alkenyl group The nadic ylidene compound is a compound represented by the formula (Ina), and the proportion of the alkenyl-substituted nadic ylidene compound is 0.01 to 1.00 by weight relative to the polyglycine or a derivative thereof, and has a radical. The ratio of the compound of the polymerizable unsaturated double bond is from 0.01 to 1.00 by weight based on the weight of the polyglycine or the derivative thereof, and the ratio of the polyglycine or the derivative thereof is 0.5 wt% in the composition. %~30 wt% (% by weight):

Wherein, L ¹ and L ² are each independently 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, and a carbon number of 6 to 12; Aryl or benzyl; n is 1 or 2; when n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a cycloalkyl group having 5 to 8 carbon atoms. An aryl group having a carbon number of 6 to 12, a benzyl group, and a group represented by -Z ¹ -(O) _q -(Z ² O) _r -Z ³ -H (in the group, Z ¹ , Z ² And Z ³ independently are an alkylene group having 2 to 6 carbon atoms, q is 0 or 1, and r is an integer of 1 to 30), and a group represented by -(Z ⁴ ) _s -BZ ⁵ -H (this In the group, Z ⁴ and Z ^{5 are} independently an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms, B is a phenylene group, and s is 0 or 1), or a group represented by -BTBH (wherein B is a phenylene group, and T is -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- or -SO ₂ -), one to three hydrogens in such W may be substituted by a hydroxyl group; when n = 2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, An arylene group having 6 to 12 carbon atoms and a group represented by -Z ¹ -(O) _q -(Z ² O) _r -Z ³ - (Z ¹ to Z ³ , q and r in the group) The meaning of Described later), to _{^{- (Z 4) s -BZ 5}} - group represented by (in the group Z ^4, meaning Z ^5, B and s as described above), or a group represented by at -BTB- ( The meaning of B and T in the group is as described above, and one to three hydrogens in such W may be substituted with a hydroxyl group.

According to the present invention, it is possible to provide a liquid crystal display element having a low ion density, good long-term reliability corresponding to variations in ion density with time, and improved afterimage characteristics.

First, the terms used in the present invention are first explained.

The "nadic ylidene compound" means a compound having the following nadic amide group.

Further, the "alkenyl-substituted nadic ylidene compound" means a compound in which the hydrogen of the nadic amide group is substituted with an alkenyl group. The substitution position of the alkenyl group is 5, 6 or 7 positions. A compound having a radical polymerizable unsaturated double bond is defined as a compound which does not include an alkenyl-substituted nadic ylidene compound. (Meth)acrylic acid is used as a general term for acrylic acid and methacrylic acid. The compound represented by the formula (1) is sometimes referred to as the compound (1). The same applies to the compounds represented by other formulas.

With regard to the side chain type diamines and the non-side chain type diamines, the definitions of these terms will be described at the outset of the relevant description of the diamines used in the present invention.

The present invention is constituted by the above item [1] and the following items [2] to [22].

[2] The liquid crystal alignment agent according to [1], which is an alkenyl-substituted nadicilimine compound, poly-proline or a derivative thereof, and a compound having a radical polymerizable unsaturated double bond. The composition, and the alkenyl-substituted nadicilide compound is at least one of the compounds represented by the formula (Ina-1) to (Ina-3):

[3] The liquid crystal alignment agent according to [1] or [2], which is an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline Or a composition of a derivative thereof, and a compound having a radical polymerizable unsaturated double bond is a (meth)acrylic acid derivative.

[4] The liquid crystal alignment agent according to [1] or [2], which is an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline Or a composition of a derivative thereof, and a compound having a radical polymerizable unsaturated double bond is a compound having two or more radically polymerizable unsaturated double bonds, or a mixture containing the compound.

[5] The liquid crystal alignment agent according to [4], which is an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a polyglycine or a derivative thereof The composition, and the compound having a radical polymerizable unsaturated double bond is N,N'-methylene bisacrylamide, N,N'-dihydroxyethylene-bis N,N'-dihydroethylene bisacrylamide, ethylene bisacrylate, and 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline) (4, At least one of 4'-methylene bis (N, N-dihydroethylene aerylate aniline).

[6] The liquid crystal alignment agent according to [1], wherein the polylysine is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting at least one of aromatic tetracarboxylic dianhydrides with a diamine, and the diamine is selected from the group consisting of non-side chain type diamines represented by formula (I) to formula (VII) At least one of:

H ₂ NX ¹ -NH ₂ (I)

Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen on the cyclohexane ring or the benzene ring may be subjected to -F, - CH _{3 is} substituted with -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ , benzyl or hydroxybenzyl.

[7] The liquid crystal alignment agent according to [1], wherein the polyamic acid is a polymer obtained by reacting an aromatic tetracarboxylic dianhydride represented by the formula (1) with a diamine, and the The diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula ( At least one of V-33) and a non-side chain type diamine represented by the formula (VII-2).

[8] The liquid crystal alignment agent according to [1], wherein the polyamic acid is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting at least one of an aromatic tetracarboxylic dianhydride and a tetracarboxylic dianhydride other than an aromatic compound with a diamine, and The diamine is at least one selected from the group consisting of non-side chain type diamines represented by the formulae (I) to (VII).

H ₂ NX ¹ -NH ₂ (I)

Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen on the cyclohexane ring or the benzene ring may be subjected to -F, -CH ₃ or -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ , benzyl or hydroxyaryl.

[9] The liquid crystal alignment agent according to [8], wherein the tetracarboxylic dianhydride other than the aromatic compound is a formula (19), a formula (23), a formula (25), and a formula (35) to a formula (37). At least one of the compounds represented by the formula (39), the formula (44), and the formula (49).

[10] The liquid crystal alignment agent according to [1], wherein the polyphthalic acid is a mixture of an aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic dianhydride other than the aromatic compound a polymer obtained by reacting a diamine, and the diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), and formula (V-). 1)~(V-12), (V-33) And at least one of the non-side chain type diamines represented by the formula (VII-2).

[11] The liquid crystal alignment agent according to [10], wherein the tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), and a formula (35) to a formula (37). At least one of the compounds represented by the formula (39), the formula (44), and the formula (49).

[12] The liquid crystal alignment agent according to [10], wherein the tetracarboxylic dianhydride other than the aromatic compound is a compound represented by the formula (19).

[13] The liquid crystal alignment agent according to [1], wherein the polyamic acid is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting at least one of an aromatic tetracarboxylic dianhydride with a diamine, and the diamine is a mixture of at least one non-side chain type diamine and at least one side chain type diamine, wherein the non- The side chain type diamine is selected from the group consisting of a non-side chain type diamine represented by the formula (I) to formula (VII), and the side chain type diamine has an alkyl group selected from a carbon number of 3 or more. An alkoxy group having 3 or more carbon atoms, an alkoxyalkyl group having 3 or more carbon atoms, a group having a steroid skeleton, and an alkyl group having a carbon number of 1 or more and a carbon at the terminal. a side chain group in the group of a ring having 1 or more alkoxy groups or an alkoxyalkyl group having 2 or more carbon atoms:

H ₂ NX ¹ -NH ₂ (I)

Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen on the cyclohexane ring or the benzene ring may be subjected to -F, -CH ₃ or -OH, -COOH, -SO ₃ H, or -PO ₃ H _2, benzyl or hydroxybenzyl.

[14] The liquid crystal alignment agent according to [13], wherein the side chain type diamine is a diamine selected from the group consisting of compounds represented by formula (VIII) to formula (XII).

(Wherein, R ¹ is a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, carbon atoms or alkylene having 1 to 6 An alkyl group, and any -CH ₂ - in the alkylene group may be substituted by -O-, -CH=CH- or -C≡C-; R ² is a group having a steroid skeleton, and the carbon number is 3 to 30 An alkyl group, a phenyl group having a carbon number of 3 to 30 or an alkoxy group having 3 to 30 carbon atoms as a substituent, or a group represented by the formula (D-1), and the alkyl group Any -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-;

Wherein R ¹³ , R ¹⁴ and R ^{15 are} independently a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxygen having 1 to 3 carbon atoms. An alkylene group or an alkyleneoxy group having a carbon number of 1 to 3; a ring B and a ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R ¹⁶ and R ^{17 are} independently a fluorine or a group a group, and m1 and m2 are independently 0, 1, or 2; e, f, and g are independently an integer of 0 to 3, and their total value is 1 or more; R ¹⁸ is an alkyl group having 1 to 30 carbon atoms. An alkoxy group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. Any of these alkyl groups, alkoxy groups and alkoxyalkyl groups may be substituted by fluorine, and optionally CH ₂ - may be substituted with a difluoromethylene group or a group represented by the formula (D-2);

Wherein R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are} independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is an integer of 1 to 100. )

(wherein R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or -CH ₂ -.)

(wherein R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or - CH ₂ -; and R ⁶ and R ^{7 are} independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group.)

(wherein R ⁸ is an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-; R ^{9 is} independently - O- or an alkylene group having a carbon number of 1 to 6; ring A is a 1,4-phenylene group or a 1,4-cyclohexylene group; a is 0 or 1; b is 0, 1 or 2; and c is independent Is 0 or 1.)

(wherein R ¹⁰ is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms; and R ¹¹ is hydrogen, an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30; A fluorinated alkyl group; R ^{12 is} independently -O- or an alkylene group having a carbon number of 1 to 6; and d is independently 0 or 1.)

[15] The liquid crystal alignment agent according to [13], wherein the side chain type diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4), formula (VIII-5), and formula (VIII-). 6) A diamine in the compound represented by the formula (X-2) and the formula (X-4).

(wherein R ²³ and R ^{24 are} independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms; and R ²⁹ and R ^{30 are} independently an alkyl group having 1 to 30 carbon atoms or a carbon number; It is an alkoxy group of 1 to 30.)

[16] The liquid crystal alignment agent according to [13], wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), and formula (IV). -16), a diamine in the compound represented by the formula (V-1) to the formula (V-12), the formula (V-33), and the formula (VII-2), and the side chain type diamine is selected from the formula ( a diamine in the compound represented by VIII-2), formula (VIII-4), formula (VIII-5), formula (VIII-6), formula (XI-2), and formula (XI-4).

(wherein R ²³ and R ^{24 are} independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms; and R ²⁹ and R ^{30 are} independently an alkyl group having 1 to 30 carbon atoms or a carbon number; It is an alkoxy group of 1 to 30.)

[17] The liquid crystal alignment agent according to [1], wherein the polyproline is selected from the group consisting of at least one aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride and at least a polymer obtained by reacting a non-side chain type diamine, and by reacting a mixture of the tetracarboxylic dianhydride with a mixture of at least one side chain type diamine and at least one of the non-side chain type diamines At least one of the obtained polymers, wherein the aromatic The tetracarboxylic dianhydride is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14), and the tetracarboxylic dianhydride other than the aromatic compound is the formula (19). , the formula (23), the formula (25), the formula (35) to the formula (37), the formula (39), the formula (44) and the formula (49), wherein the non-side chain type diamine is of the formula (IV) -1), Formula (IV-2), Formula (IV-15), Formula (IV-16), Formula (V-1) to Formula (V-12), Formula (V-33), and Formula (VII- 2) indicates that the side chain type diamine is a formula (VIII-2), a formula (VIIII-4), a formula (VIII-5), a formula (VIII-6), a formula (XI-2), and a formula ( XI-4) indicates.

(wherein R ²³ and R ^{24 are} independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms; and R ²⁹ and R ^{30 are} independently an alkyl group having 1 to 30 carbon atoms or a carbon number; It is an alkoxy group of 1 to 30.)

[18] The liquid crystal alignment agent according to [17], wherein the polyphthalic acid is a mixture of at least one aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride and at least one non- A polymer obtained by reacting a side chain type diamine.

[19] The liquid crystal alignment agent according to [17], wherein the polyproline is made of at least one aromatic tetracarboxylic dianhydride and at least one aromatic a polymer obtained by reacting a mixture of tetracarboxylic dianhydride with at least one non-side chain type diamine, and by mixing a mixture of said tetracarboxylic dianhydride with at least one non-side chain type diamine and at least one side chain A mixture of polymers obtained by reacting a mixture of diamines.

[20] The liquid crystal alignment agent according to [17], wherein the polyproline is at least one selected from the group consisting of at least one aromatic tetracarboxylic dianhydride and at least one A mixture of tetracarboxylic dianhydrides other than aromatic is obtained by reacting a mixture of at least one non-side chain type diamine and at least one side chain type diamine.

[21] A liquid crystal alignment film which is formed by applying a liquid crystal alignment agent according to [1] onto a substrate and baking it in a state of a film.

[22] A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both of opposite surfaces of the pair of substrates, and a relative of each of the pair of substrates A liquid crystal alignment film formed on the surface and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film described in the above.

Hereinafter, the liquid crystal alignment agent of the present invention will be described in detail. The liquid crystal alignment agent of the present invention is a composition containing an alkenyl-substituted nadic ylidene imine compound, a compound having a radical polymerizable unsaturated double bond, and polyglycine.

First, the alkenyl-substituted nadicilide compound is first described. Alkenyl substituted nadic quinone imine compound, preferably soluble in the hair A compound dissolved in a solvent of polylysine or a derivative thereof used. An example of such an alkenyl-substituted nadicylimine compound is a compound represented by the formula (Ina).

L ¹ and L ² in the formula (Ina) are each independently 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, n is 1 or 2.

When n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and benzyl group. a group of -Z ¹ -(O) _q -(Z ² O) _r -Z ³ -H (Z ¹ , Z ² and Z ^{3 are} independently an alkylene group having 2 to 6 carbon atoms, and q is 0 or 1 And r is an integer represented by 1 to 30), and -(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ^{5 are} independently an alkylene group having 1 to 4 carbon atoms or a carbon number of 5 a cycloalkylene group of ~8, B is a phenylene group, and s is a group represented by 0 or 1), with -BTBH (B is a phenylene group, and T is -CH ₂ -, -C(CH ₃ ) a group represented by ₂ -, -O-, -CO-, -S- or -SO ₂ -), or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group.

In this case, preferred R ³ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, and a poly(ethylene oxide) B having a carbon number of 4 to 10. a group, a phenoxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenephenyl group, and a group in which one or two hydrogens of these groups are substituted with a hydroxyl group.

When n=2 in the formula (Ina), W is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -Z group (Z ¹ ~ Z ³ and r meaning as described above) indicated to ^{-Z 4 -BZ 5 - - 1 -O-} (Z 2 O) r -Z 3 (Z 4, Z 5 , and B The meaning of the group as described above, with -B-(OB) _s -T-(BO) _s -B- (B is a phenylene group, T is an alkylene group having a carbon number of 1-3, -O - or -SO ₂ -, s is a group represented by 0 or 1), or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group.

In this case, preferred W is an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenylene group, a tolylene group, a xylylene group, and a -C ₃ H ₆ - group. O-(Z ² -O) _r -OC ₃ H ₆ -(Z ² is an alkylene group having 2 to 6 carbon atoms, and r is 1 or 2), and -BTB-(B is phenylene) a group represented by -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (B is a phenylene group), and a group of these groups One or two hydrogen-substituted groups.

Such an alkenyl-substituted nadicylimine compound can be used, for example, by maintaining an alkenyl-substituted nadic anhydride derivative and a diamine at a temperature of from 80 ° C to 220 ° C as described in Japanese Patent No. 2729565. The resulting compound is synthesized in hours to 20 hours, or a commercially available compound. Specific examples of the alkenyl-substituted nadicylimine compound include the compounds shown below.

N-methyl-allyl bicyclo[2.2.1]hept-5-ene-2,3-carboximine (N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboximide), N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine, N-methyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-methyl-methylallylmethylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine, N-(2-ethylhexyl)-allyl (methyl)bicyclo[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-allylbicyclo[ 2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-di Formamidine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine, N-cyclohexyl-allyl bicyclo [2.2. 1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-phenyl-allylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethyl Imine, N-phenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-benzyl-allyl bicyclo [2.2.1 Hept-5-ene-2,3-dimethylimine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N -benzyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-di Formamidine, N-(2-hydroxyethyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,2-di Methyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,2-dimethyl-3-hydroxypropanol (Allyl)-allyl (methyl)bicyclo[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) -allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[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 (methyl)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) )-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-carboximine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]g -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}-allyl (Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylbicyclo[ 2.2.1]hept-5-ene-2,3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine, N-{4-(4-hydroxyphenylisopropylidene) Phenyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{4-(4-hydroxyphenylisopropylidene)benzene 5-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, and their oligomers; N,N'-ethylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine) (N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboximide)), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'- Ethylene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-trimethylene-bis(allylbicyclo[ 2.2.1] hept-5-ene-2,3-dimethylimine imine), 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-dimethylimine), N , N'-docamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-dodecamethylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine), N, N'-Asia Hexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 1,2-bis{3'-(allylbicyclo[2.2.1 Hept-5-ene-2,3-dimethylimine imine)propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine imine)propoxy}ethane, 1,2-bis{3'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine) propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy }ethyl]ether, bis[2'-{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}ethyl] Ether, 1,4-double {3'-(allylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Mercaptoimine) 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]hept-5-ene-2,3-carboximine), N,N'-m-phenylene group- Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-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-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-bis ( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allyl Bicyclo[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, bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)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, double {4-(methylallyl-methyl) Bicyclo[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, bis{4-(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)phenyl}indole, double {4-(allyl Methylbicyclo[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-dimethylimine)-3- Hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-5-hydroxy-cyclohexane, 1,5-bis{3'-( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine imine) propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine)-2-hydroxy-benzene, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine)-2,5-dihydroxy-benzene, N,N'-p-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine), N,N'-p-(2-hydroxy)xylylene-bis(allyl) Base ring [2.2.1] hept-5-ene-2,3-dimethylimine), N,N'-m-(2-hydroxy)xylylene-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine), N,N'-m-(2-hydroxy)xylylene-bis(methylallylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine), N,N'-p-(2,3-dihydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine )-2-hydroxy-phenoxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)-2- Hydroxy-phenyl}methane, double {3-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo) [2.2.1]hept-5-ene-2,3-carboximine]-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)}phenoxymethylpropane, N,N',N"-tris(ethylene allylenylbicyclo[2.2.1 ]Hept-5-ene-2,3-dimethylimine imine) isocyanurate, and oligomers thereof and the like.

Further, the alkenyl-substituted nadicylimine compound used in the present invention may be a compound represented by the following structural formula containing an asymmetric alkylene group or a phenylene group.

In the present invention, these alkenyl groups may be used alone in place of the nadic ylidene imine compound, or a mixture of two or more of them may be used. Things. Preferred compounds among the alkenyl substituted nadic quinone imine compounds are listed below.

N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylidene-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'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N '-Cyclohexylene-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-carboximine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine), N,N'-m-phenylene-bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), N,N'-m-phenylene-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 -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-carboximine), N,N'-m-xylylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-bis(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-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, bis{4-(allylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Methylenimine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, double {4 -(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, double {4-( Allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine)phenyl}indole, double {4-(methyl Propyl-bicyclo [2.2.1] hept-5-ene-2,3-acyl imine) phenyl} sulfone.

More preferred alkenyl substituted nadic quinone imine compounds are listed below.

N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylidene-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-dimethylimine), N,N'-dodecamethylene - bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N' - p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-phenylene-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine), N,N'-m-phenylene-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-dimethylimine ), N, N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-xylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-m-xylylene-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]g -5-ene-2,3-dimethylimine imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylene) Propylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, double {4-(methylallyl-methyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane.

Further, a particularly preferred alkenyl-substituted nadicylimine compound can be exemplified by the following double {4-(allylbicyclo[2.2.1]hept-5-ene-2 represented by the formula (Ina-1). , 3-dimethylimine)phenyl}methane, N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene represented by formula (Ina-2) 2,3-dimethylimine), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2 represented by the formula (Ina-3), 3-dimethylimine).

Next, a compound having a radical polymerizable unsaturated double bond used in the present invention will be described. Although the alkenyl-substituted nadicilide compound also has a radically polymerizable unsaturated double bond, as described above, the compound having a radical polymerizable unsaturated double bond used in the present invention does not include an alkenyl-substituted sodium. Dickyimine compound. Such a compound having a radical polymerizable unsaturated double bond is preferably (meth) acrylate or (meth) acrylamide. (meth)acrylic acid derivatives and bismaleimide. Further, a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds is more preferable.

Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (meth)acrylic acid. Cyclopentyloxyethyl ester, isobornyl (meta) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, And 2-hydroxypropyl (meth)acrylate.

Specific examples of the difunctional (meth) acrylate include: ethylene diacrylate, products of East Asian Synthetic Chemical Co., Ltd., ARONIX M-210, ARONIX M-240, and ARONIX M-6200, Nippon Chemical Co., Ltd. Products KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kyoritsu Oil & Fat Chemical Industry Co., Ltd. Light Acrylate BA -4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline), ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylamide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, and N-n-propylmethyl Acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylamide, N - N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-diethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloyl piperidine , N-acryloyl pyrrolidine, N,N'-methylenebis propylene amide, N,N'-ethylenebis propylene amide, N,N'-dihydroxy propylene Bis-acrylamide, N-(4-hydroxyphenyl)methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl)methyl Acrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethyl Amino group )propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methylpropenamide, N-benzyl-2-methyl Acrylamide, and N,N'-methylenebismethacrylamide.

Among the above (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylidene-bisacrylamide, ethylene diacrylate, and 4 are particularly preferable. , 4'-methylenebis(N,N-dihydroxyethylene acrylate aniline).

Specific examples of the bismaleimide can be exemplified by KI CHEMICAL BMI-70 and BMI-80 manufactured by INDUSTRY Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 manufactured by Daiwa Chemical Industry Co., Ltd.

Next, the poly-proline and the derivative thereof used in the present invention will be described.

Polylysine is a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine, which is dissolved in a solvent and coated on a substrate, followed by heating, thereby being formed on the surface of the substrate. A liquid crystal alignment film formed of a polyimide film. Examples of such derivatives of polylysine are soluble polyimine, polyphthalamide, and polyamidamine. More specifically, a polyimine which is obtained by completely dehydrating and ring-closing a decyl bond and a carboxyl group of polyproline, a part in which a guanamine bond and a carboxyl group of a polyglycolic acid are partially dehydrated and closed are exemplified. Polyimine, a polyphthalate obtained by converting a carboxyl group of a polyamic acid into an ester, and a polycondensation obtained by replacing a part of a tetracarboxylic dianhydride with a dicarboxylic acid (or a halide or an acid anhydride thereof) A proline-polyamine copolymer and a polyamidoximine obtained by partially or completely dehydrating the polyamido-polyamide copolymer. Further, when a tetracarboxylic dianhydride and a dicarboxylic acid are used in combination as an acid component, not only a poly-proline-polyamine copolymer but also a polyamine and/or a poly-proline may be obtained. The mixture, in the present invention, is referred to as a poly-proline-polyamine copolymer on the premise of this possibility. In the present invention, at least one polymer selected from the group consisting of such polyamic acid and derivatives thereof is used. Moreover, it is preferred to use at least two such polymers in combination.

Tetracarboxylic dianhydride can be selected as a condition: use the four The polyamic acid obtained by the carboxylic acid dianhydride is soluble in the solvent used for the liquid crystal alignment agent. Further, among such tetracarboxylic dianhydrides, it is preferred to use at least one aromatic tetracarboxylic dianhydride. Preferred examples of the aromatic tetracarboxylic dianhydride are listed below.

Among the above aromatic tetracarboxylic dianhydrides, the compound (1), the compound (2), the compound (5), the compound (6), the compound (7), and the compound (14) are more preferable, and the compound (1) is particularly preferable. Pyromellitic dianhydride.

In the present invention, at least one of the aromatic tetracarboxylic dianhydride and at least one tetracarboxylic dianhydride other than aromatic may be used in combination. Preferred examples of the tetracarboxylic dianhydride other than aromatic are listed below.

Among the tetracarboxylic dianhydrides other than the above aromatic compounds, the compound (19) to the compound (39) and the compound (49) are more preferable, and the compound (19), the compound (23), the compound (25), and the compound (35) are more preferable. - Compound (37), Compound (39), Compound (44), and Compound (49). Further, the compound (19) (1,2,3,4-cyclobutanetetracarboxylic dianhydride) is particularly preferred.

On the other hand, in order to form the polyaminic acid of the present invention or a derivative thereof into a solvent-soluble polyimine, it is preferred to use the formula (24), the formula (35) to the formula (44), and the formula ( 49) A tetracarboxylic dianhydride represented by the formula (50), the formula (53), and the formula (60).

Further, in the present invention, it is preferred to use at least one of the aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride in combination. It is also preferred to use the compound (1) (pyromellitic dianhydride) and the compound (19) (1,2,3,4-cyclobutanetetracarboxylic dianhydride) in combination. When a liquid crystal alignment film is formed using the liquid crystal alignment agent containing the polyamic acid and the compound (A) thus obtained, it is possible to impart good long-term reliability in accordance with the voltage holding ratio to the liquid crystal display element including the liquid crystal alignment film.

Further, as the tetracarboxylic dianhydride in the present invention, other tetracarboxylic dianhydrides other than the compound (1) to the compound (67) can be used. Other tetracarboxylic dianhydrides can be arbitrarily selected as long as the object of the present invention is achieved, and various forms of tetracarboxylic dianhydride can be used. For example, tetracarboxylic dianhydride having a side chain structure can also be used. When a polyphthalic acid obtained by using a tetracarboxylic dianhydride having a side chain structure is used in a liquid crystal alignment agent, a liquid crystal alignment film formed of the liquid crystal alignment agent can increase a liquid crystal display element containing the liquid crystal alignment film. Pretilt angle.

The tetracarboxylic dianhydride having a side chain structure is not particularly limited, and preferred examples thereof include a compound (68) having a steroid skeleton and a compound (69).

In the present invention, a part of the tetracarboxylic dianhydride may be used instead of the carboxylic anhydride. By replacing a part of the tetracarboxylic dianhydride with a carboxylic acid anhydride, the polymerization reaction can be terminated, and the reaction can be further suppressed, so that the molecular weight of the obtained polyamic acid can be easily controlled. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride is not particularly limited as long as the effect of the present invention is not impaired, and 10 mol% (mol%) or 10 mol% or less of the total amount of the tetracarboxylic dianhydride is preferable.

Any diamine can be used in the present invention. However, in the case of a VA type liquid crystal display element, a large pretilt angle of about 80 to 90 degrees is required, and in the case of an OCB type liquid crystal display element, a pretilt angle of about 7 to 20 degrees is often required, and a TN type liquid crystal display is required. In the case of an element or an STN liquid crystal display element, a pretilt angle of about 3° to 10° is required, and in the case of an IPS type liquid crystal display element, a small pretilt of about 0° to 3° is required. angle. Therefore, the adjustment of the pretilt angle must be considered.

Further, diamines can be classified into two types depending on the difference in their structures. That is, when the skeleton linking the two amino groups is regarded as the main chain, the diamine is divided into a diamine having a group branched from the main chain, that is, a side chain group and a second group having no side chain group. amine. By reacting a diamine having a side chain group with a tetracarboxylic dianhydride, polylysine or polyimine having a plurality of side chain groups with respect to the polymer main chain can be obtained. When such a polyamic acid or a polyimine having a side chain group with respect to a polymer main chain is used, a liquid crystal alignment film formed of a liquid crystal alignment agent containing the polymer can increase a liquid crystal display element. Pretilt angle. That is, the above-mentioned side chain group is a group having an effect of increasing the pretilt angle, and is selected from an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, and a carbon number of 3 or more or more alkoxyalkyl groups, a group having a steroid skeleton, and an alkoxy group having a carbon number of 1 or 1 or more, a carbon number of 1 or more or a carbon number of 2 or 2 or more of the groups of the alkoxyalkyl group. The diamine having such a side chain group is referred to as a side chain type diamine in the present invention. A diamine having no such a side chain group is referred to as a non-side chain type diamine.

Further, by appropriately combining the side chain type diamine and the non-side chain type diamine, it is possible to correspond to the pretilt angle required for each of the above various display elements. That is, when a large pretilt angle is not required, it is sufficient to use at least one non-side chain type diamine. In the case of use of the above-described VA liquid crystal display device, OCB liquid crystal display device, or STN liquid crystal display device, at least one non-side chain type diamine and at least one side chain type diamine may be used in combination. At this time, the ratio of the non-side chain type diamine to the side chain type diamine is as long as the target is The size of the pretilt angle can be determined. Of course, by appropriately selecting the side chain groups, it is also possible to use only the side chain type diamine to correspond to the desired pretilt angle. Thus, the liquid crystal alignment agent of the present invention can be applied to any type of liquid crystal display element. In addition, the effect of such side chain groups is also the same for the tetracarboxylic dianhydride.

Specific examples of the side chain groups are as follows.

First, the first one can be exemplified: alkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl And alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like. Further, the alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having a carbon number of 3 or more. However, the alkoxyalkyl group may have a total carbon number of 3 or more. Further, these groups may be linear or branched.

Next, when the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, Examples thereof include a phenyl group, a phenylalkyl group, a phenylalkoxy group, a phenoxy group, a phenylcarbonyl group, a phenylcarbonyloxy group, a phenoxycarbonyl group, a phenylaminocarbonyl group, a phenylcyclohexyloxy group, and a carbon number. Is 3 or more cycloalkyl, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy , bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, and cyclohexyl A group having a ring structure such as bis(phenyl)oxycarbonyl. In addition, bis(cyclohexyl) And bis(phenyl) can also be bonded via an alkylene group instead of a single bond, respectively.

Further, a collection ring group may be mentioned: two or more benzene rings or a cyclohexane ring through a single bond, -O-, -COO-, -OCO-, -CONH- or a carbon number of 1~ The alkylene group of 3 is bonded, and the terminal ring has an alkyl group having 3 or more carbon atoms, a fluorine-substituted alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, Or an alkoxyalkyl group having 3 or more carbon atoms as a substituent. Of course, groups having a steroid backbone are also effective side chain groups.

Preferred examples of the non-side chain type diamine are listed below.

H ₂ NX ¹ -NH ₂ (I)

Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be subjected to -F, -CH ₃ or -OH, -COOH, -SO ₃ H, or -PO ₃ H _2, benzyl or hydroxybenzyl.

Preferred examples of the diamine represented by the formula (I) are listed below.

Preferred examples of the diamine represented by the formula (II) are listed below.

Preferred examples of the diamine represented by the formula (III) are listed below.

Preferred examples of the diamine represented by the formula (IV) are listed below.

Preferred examples of the diamine represented by the formula (V) are listed below.

Preferred examples of the diamine represented by the formula (VI) are listed below.

Preferred examples of the diamine represented by the formula (VII) are listed below.

More preferable examples of these diamines are the compound (IV-1) to the compound (IV-5), the compound (IV-15), the compound (IV-16), and the compound (V-1) to the compound (V-12). ), Compound (V-26), Compound (V-27), Compound (V-31), Compound (V-33), Compound (VI-1), Compound (VI-2), Compound (VI-6) And a compound (VII-1) to a compound (VII-5), and particularly preferable examples are the compound (IV-1), the compound (IV-2), the compound (IV-15), the compound (IV-16), and the compound. (V-1)~ Compound (V-12), Compound (V-33), and Compound (VII-2).

Specific examples of the side chain type diamine used in the present invention include diamines represented by the following formulas (VIII) to (XII).

In the formula (Ⅷ), R ¹ is a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or a carbon number of 1 ~ An alkylene group of 6, any -CH ₂ - in the alkylene group may be substituted by -O-, -CH=CH- or -C≡C-; R ² is a group having a steroid skeleton, and the carbon number is a 3 to 30 alkyl group, a phenyl group having a carbon number of 3 to 30 or an alkoxy group having 3 to 30 carbon atoms as a substituent, or a group represented by the formula (D-1), Any -CH ₂ - in the alkyl group may be substituted with -O-, -CH=CH- or -C≡C-.

Wherein R ¹³ , R ¹⁴ and R ^{15 are} independently a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxygen having 1 to 3 carbon atoms. An alkylene group or an alkyleneoxy group having a carbon number of 1 to 3; a ring B and a ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R ¹⁶ and R ^{17 are} independently a fluorine or a group a group, and m1 and m2 are independently 0, 1, or 2; e, f, and g are independently an integer of 0 to 3, and their total value is 1 or more; R ¹⁸ is an alkyl group having 1 to 30 carbon atoms. An alkoxy group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. Any of these alkyl groups, alkoxy groups and alkoxyalkyl groups may be substituted by fluorine, and optionally -CH ₂ - may be substituted with a difluoromethylene group or a group represented by the formula (D-2).

Wherein R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are} independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is an integer of 1 to 100.

Wherein R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or -CH ₂ -. Preferably, one of the two aminophenyl-R ⁵ -O- groups is bonded to the 3 position of the steroid backbone and the other is bonded to the 6 position. Further, it is preferred that the bonding positions of the two amino groups on the benzene ring are each a meta or a para position with respect to the bonding position of R ⁵ . Further, any hydrogen which is bonded to the carbon forming the steroid skeleton may be substituted with a methyl group.

Wherein R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or -CH ₂ -; and, R ⁶ and R ^{7 are} independently hydrogen, alkyl having 1 to 30, or a phenyl group. The bonding positions of the two R ⁷ -substituted aminophenyl-R ⁵ -O- groups on the phenyl ring are preferably each a meta or para position relative to the carbon to which the steroid backbone is bonded. Further, the bonding positions of the two amino groups on the benzene ring are preferably each a meta or para position with respect to R ⁵ .

Wherein R ⁸ is an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-; R ^{9 is} independently -O - or an alkylene group having a carbon number of 1 to 6; ring A is a 1,4-phenylene group or a 1,4-cyclohexylene group; a is 0 or 1; b is 0, 1 or 2; and, c is independent It is 0 or 1. The bonding positions of the two amino groups on the benzene ring are preferably each a meta or para position relative to R ⁹ .

Wherein R ¹⁰ is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms; and R ¹¹ is hydrogen, an alkyl group having 1 to 30 carbon atoms or a fluorine having 1 to 30 carbon atoms; Alkyl; R ^{12 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; and d is independently 0 or 1. The bonding positions of the two amino groups on the phenyl ring are preferably each a meta or para position relative to R ¹² .

Examples of the diamine represented by the formula (VIII) include a diamine represented by the formula (VIII-1) to the formula (VIII-43).

In the formulae (VIII-1) to (VIII-11), R ²³ and R ²⁴ are each preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably 5 carbon atoms. ~25 alkyl or alkoxy having 5 to 25 carbon atoms.

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

In the formulae (VIII-18) to (VIII-37), R ²⁷ and R ²⁸ are each preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms. 25 alkyl or an alkoxy group having 5 to 25 carbon atoms.

Among the above diamines, a diamine represented by the formula (VIII-1) to the formula (VIII-11) is preferred, and a formula (VIII-2), a formula (VIII-4), a formula (VIII-5) and a formula are more preferred. A diamine represented by any one of (VIII-6).

Examples of the diamine represented by the formula (IX) include a diamine represented by the formula (IX-1) to the formula (IX-4).

Examples of the diamine represented by the formula (X) include a diamine represented by the formula (X-1) to the formula (X-8).

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

In the formula (XI-1) to the formula (XI-3), R ²⁹ is preferably an alkyl group having 1 to 30 carbon atoms, and in the formula (XI-4) to the formula (XI-8), R ³⁰ is preferably a carbon number. It is an alkyl group of 1 to 20.

Examples of the diamine represented by the formula (XII) include a diamine represented by the formula (XII-1) to the formula (XII-3).

In these formulas, R ³¹ is preferably an alkyl group having 6 to 20 carbon atoms, and R ³² is preferably hydrogen or an alkyl group having 1 to 10 carbon atoms.

In the present invention, other diamines other than the diamine represented by the formula (I) to the formula (XII) may be used in combination. Examples of such other diamines include naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, and fluorene-based diamines having a siloxane coupling. The amine may also have a side chain group.

A preferred example of the decane-based diamine is a compound represented by the following formula (XV).

In the formula (XV), R ³³ and R ³⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and X ^{4 is} independently an alkylene group having 1 to 6 carbon atoms or a phenylene group, and m is 1 An integer of ~10. Further, any hydrogen of the phenylene group may be substituted with an alkyl group having 1 to 4 carbon atoms.

A preferred example of the other diamines is a compound represented by the following formula (1') to formula (8'), in addition to the alkoxyalkylene-based diamine.

In these formulas, R ³⁵ and R ³⁶ are each independently an alkyl group having 3 to 30 carbon atoms.

In the present invention, a monoamine can be used in addition to the diamine. By using a monoamine, the polymerization reaction can be terminated, so that the reaction can be further inhibited, so that the molecular weight of the polymer (polyproline) can be easily controlled. The ratio of the monoamine to the diamine may be within a range that does not impair the effects of the present invention, and is preferably 10 mol% (mol%) or 10 mol% or less based on the total amount of the amine.

The polyproline or the derivative thereof in the present invention may have any weight average molecular weight. The weight average molecular weight of the polyamic acid or a derivative thereof is not particularly limited, and when used as a component of the liquid crystal alignment agent, it is preferably 5 × 10 ³ or 5 × 10 ³ or more, more preferably 1 × 10 ⁴ or 1 ×. 10 ⁴ or more. The polyglycine having a weight average molecular weight of 5 × 10 ³ or 5 × 10 ³ or more or a derivative thereof does not evaporate in the step of firing the liquid crystal alignment film, and has excellent physical properties as a component of the liquid crystal alignment agent.

The polyproline or the derivative thereof in the present invention may have any weight average molecular weight. The weight average molecular weight of the polyamic acid or a derivative thereof is not particularly limited, and when used as a component of the liquid crystal alignment agent, it is preferably 5 × 10 ³ or 5 × 10 ³ or more, more preferably 1 × 10 ⁴ or 1 ×. 10 ⁴ or more. The polyglycine having a weight average molecular weight of 5 × 10 ³ or 5 × 10 ³ or more or a derivative thereof does not evaporate in the step of firing the liquid crystal alignment film, and has excellent physical properties as a component of the liquid crystal alignment agent.

The weight average molecular weight is determined by a gel permeation chromatography (GPC) method. For example, the obtained polyglycine or a derivative thereof is diluted with dimethylformamide (DMF) to a polymer concentration of about 1 wt%, and then a 2695 separation module is used. And a 2414 differential refractometer (manufactured by Waters Co., Ltd.), DMF was used as a developing solvent, and measured by a gel permeation chromatography (GPC) method, and the weight average molecular weight was determined by polystyrene conversion. In addition, in order to accurately measure GPC such as polyacrylic acid or polyacrylic acid, inorganic acids such as phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid, or inorganic substances such as lithium bromide and lithium chloride may be prepared. A developing solvent in which a salt is dissolved in a DMF solvent.

The polyaminic acid or a derivative thereof in the present invention can be produced by a known method. For example, it has a raw material supply port, a nitrogen gas inlet, and In a reaction vessel of a thermometer, a stirrer, and a condenser, a desired amount of at least one diamine represented by the formula (I) to the formula (XII) is added, and a desired amount of at least one selected from the other diamines is optionally added. The amine is additionally added in the required amount of monoamine as needed.

Next, a solvent (for example, a guanamine-based polar solvent such as N-methyl-2-pyrrolidone or dimethylformamide) and one or two or more kinds of tetracarboxylic acids are added. The dianhydride is additionally added with a carboxylic anhydride as needed. In this case, the total addition amount of the tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of the diamine (molar ratio is about 0.9 to 1.1).

A solution of polyglycine can be obtained by reacting at a temperature of from 0 ° C to 70 ° C for 1 hour to 48 hours under stirring. Further, it is also possible to obtain a polylysine having a small molecular weight by heating and increasing the reaction temperature (for example, 50 ° C to 80 ° C). The obtained solution of polylysine can be used after dilution with a solvent to adjust to a desired viscosity.

The polyproline is precipitated by using a large amount of a poor solvent, and the solid component and the solvent are completely separated by filtration or the like, and then passed through infrared spectroscopy (IR), nuclear magnetic resonance (NMR) (Nuclear Magnetic Resonance, NMR). The analysis identified polylysine. In addition, after decomposing the solid polyamic acid in an aqueous solution of a strong alkali such as KOH or NaOH, extraction is carried out with an organic solvent, and gas chromatography (GC) and high performance liquid chromatography (HPLC) are performed. Or Gas Chromatography-Mass Spectrometry (GC-MS) analysis, whereby the monomers used can be identified.

When the poly-proline in the present invention is a poly-proline derivative, that is, a soluble polyimine, an acid anhydride solution such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as a dehydrating agent and a dehydrating agent. A closed-loop catalyst, that is, a tertiary amine such as triethylamine, pyridine or collidine, is obtained by carrying out a hydrazine imidization reaction at a temperature of from 20 ° C to 150 ° C.

It is also possible to use a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a glycol solvent) to precipitate the polyamic acid from the polyaminic acid solution and to precipitate the precipitated polymer. The valine acid is obtained by performing a hydrazine imidization reaction in a solvent such as toluene or xylene with a dehydrating agent and a dehydration ring-closure catalyst as described above at a temperature of from 20 ° C to 150 ° C.

In the hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closure catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and the dehydration ring-closure catalyst to be used is preferably 1.5 to 10 times by mole based on the total molar amount of the acid dianhydride contained in the tetracarboxylic dianhydride to be used. By adjusting the chemical hydrazide dehydrating agent, the amount of the catalyst, the reaction temperature, and the reaction time, the degree of hydrazide can be controlled to obtain a partial polyimine.

The obtained polyimine can be separated from the solvent and then redissolved in a solvent to be used as a liquid crystal alignment agent together with a modifier, wherein the modifier is a substituted naphthyl imine compound and the selected one. The modifier may be added from at least one of the heterocyclic compounds 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 replaced with an organic dicarboxylic acid. If using organic dicarboxylic acids And the tetracarboxylic dianhydride to produce the poly-proline of the present invention, then 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 that does not impair the effects of the present invention, and the basis thereof is preferably 10 mol% or less.

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

Next, the liquid crystal alignment agent of the present invention will be described. The liquid crystal alignment agent of the present invention is a composition containing an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline or a derivative thereof. The liquid crystal alignment agent of the present invention may further contain a solvent, or may further contain various additives contained in a general liquid crystal alignment agent, from the viewpoints of physical properties such as viscosity, ease of use, and simplification of the steps.

From the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the ratio of the alkenyl group substituted nadic ruthenium compound in the liquid crystal alignment agent of the present invention is relative to the polylysine or its derivative in the liquid crystal alignment agent. The weight ratio is preferably 0.01 to 1.00, more preferably 0.01 to 0.70, still more preferably 0.01 to 0.50.

From the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the ratio of the compound having a radical polymerizable unsaturated double bond in the liquid crystal alignment agent of the present invention in a weight ratio relative to polyglycine or a derivative thereof It is preferably 0.01 to 1.00, more preferably 0.01 to 0.70, still more preferably 0.01 to 0.50.

From reducing the ion density of the liquid crystal display element and suppressing the ion density From the viewpoint of increasing the time and suppressing the afterimage, the ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadic ylidene compound is preferably 0.1 to 10, more preferably 0.5 to the weight ratio. 5.

The content ratio of the polyamic acid or the 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 step of a general liquid crystal display element (including an offset printer and an inkjet printer. Hereinafter, simply referred to as a "printing machine"), a liquid crystal alignment agent. The content of the poly-proline or the derivative thereof is preferably 0.5% by weight to 30% by weight based on the total amount, and more preferably 1% by weight to 15% by weight based on the total amount, but it is considered It is appropriately adjusted in relation to 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 or a use of a polymer component such as polyacrylamide, soluble polyimine, or polyamidoximine, and is appropriately selected depending on the purpose of use. The solvent is preferably a mixed solvent containing 1) an aprotic polar organic solvent which is easily soluble for polyphthalic acid or soluble polyimide, and 2) a solvent which changes surface tension to improve coatability and the like. These solvents are exemplified below.

1) An aprotic polar organic solvent (hereinafter referred to as an aprotic polar organic solvent) which is a good solvent for polyaminic acid or soluble polyimine: for example, N-methyl-2-pyrrolidone, dimethyl Dimethyl imidazolidinone, N-methyl caprolactam, N-methyl propionamide, N,N-dimethylacetamide, dimethyl Dimethyl sulfoxide, N, N- Dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone, and γ-valerolactone. Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, and γ-valerolactone are preferable.

2) A solvent (hereinafter referred to as another solvent) which changes the surface tension to improve coating properties and the like: for example, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone ( Isophorone), ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl ether or phenyl ether acetate, triethyl a dipropylene glycol monoalkyl ether such as a diol monoalkyl ether or a propylene glycol monoalkyl ether such as propylene glycol monobutyl ether; a dialkyl malonate such as diethyl malonate; or a dipropylene glycol monomethyl ether; Their ester compounds such as acetates. Among these solvents, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are preferable.

The type and ratio of the aprotic polar solvent and other solvents can be appropriately set in consideration of printability, coatability, solubility, storage stability, and the like of the liquid crystal alignment agent. The aprotic polar solvent is relatively superior in solubility and storage stability as compared with other solvents, and the other solvents are excellent in printability and coatability.

As described above, the liquid crystal alignment agent of the present invention may also contain various additives. Various additives may be selected from polymer compounds other than polyamine or derivatives thereof, or low molecular compounds, depending on the respective purpose.

For example, a polymer which is soluble in an organic solvent can also be used as an additive, and by adding these additives, the formed liquid crystal can be controlled. Electrical properties or alignment to the film. Examples of such polymers include polyamines, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, and ketones. Polyurethane and anthrone modified polyester.

Further, for the low molecular compound additive, for example, 1) an interfacial agent may be used in accordance with the purpose when it is desired to improve the coatability, 2) an antistatic agent may be used when it is necessary to improve the antistatic property, and 3) when it is desired to improve the substrate A decane coupling agent or a titanium coupling agent may be used for the adhesion or rubbing resistance, and 4) a hydrazine imidization catalyst may be used when the hydrazine imidization is carried out at a low temperature.

Examples of the decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy decane, and N- (2-Aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-amino Phenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl Methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylidene)-3-(triethoxydecylalkyl)- 1-propylamine, N,N'-bis[3-(trimethoxydecyl)propyl]ethylenediamine, and the like.

An example of the ruthenium amide catalyst is preferably an aliphatic amine such as trimethylamine, triethylamine, tripropylamine or tributylamine; N,N-dimethylaniline, N,N- Aromatic amines such as diethyl aniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl A catalyst such as a cyclic amine such as an isoquinoline, a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole or a hydroxy-substituted imidazole. Specific examples thereof include N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline.

The amount of the decane coupling agent to be added is usually from 0 to 0.10, preferably from 0.001 to 0.03, based on the weight ratio of the polyamic acid or the derivative thereof.

The amount of the ruthenium imidization catalyst to be added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, to the carbonyl group of the polyglycine or a derivative thereof.

The amount of the other additives to be added varies depending on the use, and is usually from 0 to 0.30, preferably from 0.001 to 0.10, based on the weight ratio of the polyglycine or the derivative thereof.

Another preferred embodiment of the liquid crystal alignment agent of the present invention is a composition containing two or more kinds of polyamic acid. For example, a liquid crystal alignment agent containing a first polyamic acid and a second polyamic acid, wherein the first polyamic acid is a tetracarboxylic dianhydride and a diamine, and a compound having a side chain group is not used. Further, the second poly-proline is obtained by using one of the tetracarboxylic dianhydride and the diamine or a compound having a side chain group. More specifically, one of the polylysines is at least one aromatic tetracarboxylic dianhydride (preferably the compound (1) to the compound (18)) and at least one aromatic tetracarboxylic acid One or both of a dianhydride (preferably the compound (19) to the compound (67)), and at least one non-side chain type diamine (preferably a polylysine obtained by reacting the compound (I) to the compound (VII) or a derivative thereof (hereinafter sometimes referred to as "polyamido acid I"), and another poly-proline is the aromatic tetracarboxylic acid One or both of acid dianhydride and tetracarboxylic dianhydride other than aromatic, and at least one side chain type diamine (preferably compound (VIII) to compound (XII), or at least one of the side chain type diamines and Polylysine obtained by reacting at least one mixture of non-side chain type diamines or a derivative thereof (hereinafter sometimes referred to as "polyglycolic acid II").

The composition containing polylysine I and polyphthalic acid II of the present invention is prepared by mixing the polyaminic acid I and polylysine II. The weight ratio of the mixed polyaminic acid I to polylysine II is preferably I/II = 99/1 to 50/50, more preferably I/II = 95/5 to 80/20. The weight ratio may be appropriately adjusted according to the required pretilt angle, and if the ratio of the polyamic 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 polyamic acid II, and may further contain polyamic acid other than polyamine acid I and polyamine acid II or a derivative thereof.

On the other hand, the polyamic acid II has an effect of imparting a suitable pretilt angle to a liquid crystal display element containing a liquid crystal alignment film which is a liquid crystal alignment agent containing the polyamic acid II. Forming. When the polyamic acid II is synthesized, a diamine other than the diamine having a side chain may be used in combination. Examples of the diamine which can be used in combination include the above-mentioned compound (I) to the compound (VII), an anthracene diamine, and a decane-based diamine.

By combining (blending) the polyamic acid I and polyphthalic acid II, it is possible to impart excellent characteristics as a liquid crystal alignment agent of the present invention. Specifically, The liquid crystal alignment film formed using the composition of the present invention is imparted with better long-term reliability by appropriately selecting the kind of the diamine to be used and a combination thereof for the diamine which is a raw material of polylysine. A suitable pretilt angle.

The liquid crystal alignment film of the present invention can be formed, for example, by applying the liquid crystal alignment agent of the present invention to a substrate for a liquid crystal display element or a substrate for measurement such as calcium fluoride or ruthenium, and then applying the liquid crystal alignment agent. The film is heated to, for example, 150 ° C to 400 ° C, preferably 180 ° C to 280 ° C. Here, the film thickness of the liquid crystal alignment film is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. Further, the liquid crystal alignment film is preferably subjected to a rubbing treatment.

The film thickness of the liquid crystal alignment film can be adjusted according to the viscosity of the liquid crystal alignment agent or the coating method of 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 profilometer or an ellipsometer. Further, the components in the liquid crystal alignment film may be subjected to hydrolysis or the like as needed, and analyzed by an ordinary analytical method such as IR or MS.

The liquid crystal display device of the present invention comprises: 1) a pair of substrates disposed oppositely, 2) a liquid crystal alignment film of the present invention formed on a surface facing each of the pair of substrates, and 3) sandwiched between A liquid crystal layer between a pair of substrates.

The pair of electrode-attached substrates disposed opposite each other is 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 correspondence 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 indium tin oxide (ITO) or a vapor deposited film of a metal. The electrode may be formed on the entire surface of the substrate or may be formed, for example, in a patterned specific shape. The substrate on which no electrode is provided is a liquid crystal alignment film of the present invention formed on the surface of the substrate, and the substrate on which the electrode is provided is a liquid crystal alignment film of the present invention formed on the electrode. 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 contains a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and 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. Any composition.

An example of a 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 8-157826 Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei 9-241644 (EP 885 272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), and Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1) 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), Japanese Patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The liquid crystal composition used in the VA liquid crystal display element may be various liquid crystal compositions having a negative dielectric anisotropy. An example of a liquid crystal composition is disclosed in Japanese Laid-Open Patent Publication No. Sho 57-114532, Japanese Patent Laid-Open No. Hei No. 2-4725, Japanese Patent Application Laid-Open No. Hei-4-224885 Japanese Patent Laid-Open No. Hei 10-104076, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Publication No. Hei 10-168453 Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei 10--237000, Japanese Patent Laid-Open No. Hei 10-237004, Japan Japanese Laid-Open Patent Publication No. Hei 10-237025, 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 (EP967261A1) Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10-291945, and Japanese Patent Laid-Open No. Hei 11-029581 Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2001-192. Bulletin, etc.

In the liquid crystal composition in which the dielectric anisotropy is positive or negative, one or more optically active compounds may be added and used.

The liquid crystal display element of the present invention may of course contain other members. For example, in a TFT-type liquid crystal element using a color display of a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like can be formed on the first transparent substrate, and on the second transparent substrate. A black matrix, a color filter, a planarization film, a pixel electrode, and the like that shield light outside the primitive region.

Further, in the VA liquid crystal display device, particularly the MVA liquid crystal display device, a microscopic projection called a domain is formed on the first transparent substrate. Further, a spacer for adjusting a cell gap of the liquid crystal cell between the substrates may be formed.

The liquid crystal display element of the present invention is 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) drying the applied liquid crystal alignment agent. 3) performing necessary heat treatment on the dried liquid crystal alignment agent to perform dehydration and ring closure reaction; 4) orienting the obtained alignment film; and 5) adhering the two substrates while maintaining a specific gap Then, 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.

The coating method in the step of coating the liquid crystal alignment agent is generally known as a spinner method, a printing method, a dipping method, a falling-drop method, an inkjet method, or the like. These methods can also be used in the present invention.

Further, the drying step and the method of performing the heat treatment step necessary for the dehydration reaction are generally known in an oven or an infrared furnace. A method of performing heat treatment, a method of performing heat treatment on a hot plate, or the like. These methods can also be used in the present invention. The drying step is preferably carried out at a lower temperature (50 ° C to 140 ° C) in the range in which the solvent can be evaporated. The step of heat treatment is usually preferably carried out at a temperature of from about 150 ° C to about 300 ° C.

For 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, the alignment treatment of the liquid crystal alignment film is usually performed by rubbing treatment. Most of the VA liquid crystal display elements are not subjected to rubbing treatment, but rubbing treatment may be performed.

Next, an adhesive is applied onto one of the substrates and bonded, and liquid crystal is injected in a vacuum. In the case of the drop dropping method, the liquid crystal is dropped onto the substrate before bonding, and then the other substrate is bonded. The liquid crystal display element of the present invention is produced by hardening the 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 can be mounted on 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 these examples. The compounds used in the examples are as follows.

<tetracarboxylic dianhydride>

Compound (1): pyromellitic dianhydride

Compound (19): 1,2,3,4-cyclobutanetetracarboxylic dianhydride

Compound (23): 1,2,3,4-butanetetracarboxylic dianhydride

<Diamine>

Compound (V-1): 4,4'-diaminodiphenylmethane

Compound (V-7): 1,2-bis(4-aminophenyl)ethane

Compound (VII-2): 1,3-bis(4-(4-aminobenzyl)phenyl)propane

Compound (XI-6-1): 1,1-bis[4-(4-aminophenoxy)phenyl]-4-[(4-heptylcyclohexyl)ethyl]cyclohexane

Compound (XI-4-1): 1,1-bis[4-(4-aminophenoxy)phenyl-4-(trans-4-n-pentylcyclohexyl)cyclohexane

Compound (XI-6-2): 1,1-bis[4-(4-aminophenoxy)phenyl]-4-[(4-ethylcyclohexyl)ethyl]cyclohexane

Compound (XI-2-1): 1,1-bis[4-(4-aminophenyl)methylphenyl]-4-n-pentylcyclohexane

<Alkenyl substituted nadic ylidene compound>

Compound (Ina-1): bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane

<Compound having a radical polymerizable unsaturated double bond>

EBA: ethylene diacrylate

NEBA: N, N'-ethylene bis acrylamide

HEA: N, N'-dihydroxyethylene bis acrylamide

MHA: 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline)

<solvent>

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

[Synthesis Example 1] (Synthesis of polylysine)

Compound (V-1) (2.91 g), dehydrated NMP (54 g) and GBL (15 g) were added to a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material addition port, and a nitrogen inlet, under a dry nitrogen stream. Stir and dissolve. Next, the compound (19) (1.01 g) and the compound (1) (2.08 g) were added, and the mixture was reacted at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction is carried out by suppressing the reaction temperature to about 70 ° C or lower. Then, BC (25 g) was added to the obtained solution to prepare a polyglycine solution (PA1) having a concentration of 6 wt%. The polyamic acid obtained had a weight average molecular weight of 57,000.

The weight average molecular weight of polylysine is determined by diluting the obtained polyamic acid with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100 by weight ratio) to cause polymerization. The concentration of valine was about 1 wt%, and then the mixed solution was used as a developing solvent using a 2695 separation module and a 2414 differential refractometer (manufactured by Waters), and the mixture was measured by a GPC method, and then converted into polystyrene. Further, the column was measured using HSPgel RT MB-M (manufactured by Waters) under the conditions of a column temperature of 40 ° C and a flow rate of 0.35 mL / min.

[Synthesis Example 2 to Synthesis Example 8]

In addition to changing the tetracarboxylic dianhydride and the diamine as shown in Table 1, Synthesis Example 1 As a standard, a polyamic acid solution (PA2) to a polyaminic acid solution (PA8) was prepared. Including Synthesis Example 1, the blending ratio of the raw materials and the weight average molecular weight of the obtained polyglycine were summarized in Table 1.

[Example 1] (Production of liquid crystal display element)

The polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA2) having a concentration of 6 wt% prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, the ratio is 10 parts by weight per 100 parts by weight of the polyglycolic acid. For example, a compound in which an alkenyl group is substituted with a nadic ylidene compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, MHA are separately added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced using the obtained liquid crystal alignment agent, and the manufacturing method was as follows.

The liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode 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, and then heat-treated at 210 ° C for 20 minutes, followed by rubbing treatment to form a liquid crystal alignment film. After ultrasonic cleaning of the substrate in ultrapure water for 5 minutes, it was dried in an oven at 120 ° C for 30 minutes.

A gap material of 7 μm was spread on one of the glass substrates, and another glass substrate was disposed opposite to the inner side of the surface on which the liquid crystal alignment film was formed so that the rubbing direction was antiparallel. Then, an epoxy hardener was used to seal the periphery of the liquid crystal alignment film to form an antiparallel cell having a gap of 7 μm. A liquid crystal composition shown below was injected into this liquid crystal cell, and then a light hardening agent was used to seal the injection port for the liquid crystal composition. Then, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element.

<Liquid crystal composition>

[Embodiment 2]

The polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA3) having a concentration of 6 wt% prepared in Synthesis Example 3 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl-substituted nadic quinone imine compound (Ina-1) and a radical are respectively added in a ratio of 10 parts by weight per 100 parts by weight of the polyaminic acid. The compound which is a polymerizable unsaturated double bond is HEA. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. 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 polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA2) having a concentration of 6 wt% prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl-substituted nadic quinone imine compound (Ina-1) and a radical are respectively added in a ratio of 10 parts by weight per 100 parts by weight of the polyaminic acid. The compound which is a polymerizable unsaturated double bond is NEBA. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. 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 polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA2) having a concentration of 6 wt% prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl-substituted nadic quinone imine compound (Ina-1) and a radical are respectively added in a ratio of 10 parts by weight per 100 parts by weight of the polyaminic acid. The compound which is a polymerizable unsaturated double bond, that is, MHA, has a total amount of the modifier composed of these compounds of 20 parts by weight. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole solution 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. Pieces.

[Example 5]

In the polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4, an alkenyl group was substituted with Nadick, respectively, in a ratio of 10 parts by weight per 100 parts by weight of the polyglycolic acid. The quinone imine compound is a compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, MHA. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 6]

In the polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4, an alkenyl group was substituted with Nadick, respectively, in a ratio of 10 parts by weight per 100 parts by weight of the polyglycolic acid. The quinone imine compound is a compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, EBA. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 7]

The polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA6) having a concentration of 6 wt% prepared in Synthesis Example 6 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl group-substituted nadic ylidene compound, that is, a compound (Ina-1), is separately added. And a compound having a radically polymerizable unsaturated double bond, that is, HEA, wherein 20 parts by weight of the compound (Ina-1) is added per 100 parts by weight of the polyglycolic acid, and 5 parts by weight of HEA is added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole solution 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]

The polyglycine solution (PA5) having a concentration of 6 wt% prepared in Synthesis Example 5 and the polyglycine solution (PA6) having a concentration of 6 wt% prepared in Synthesis Example 6 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl-substituted nadic ylidene compound, that is, a compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, HEA, are added, respectively, wherein the polymer is present per 100 parts by weight of the polyfluorene. Amino acid, 20 parts by weight of the compound (Ina-1) was added, and 5 parts by weight of HEA was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole solution 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 9]

The polyglycine solution (PA5) having a concentration of 6 wt% prepared in Synthesis Example 5 and the polyglycine solution (PA7) having a concentration of 6 wt% prepared in Synthesis Example 7 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl-substituted nadic ylidene compound, that is, a compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, HEA, are added, respectively, wherein the polymer is present per 100 parts by weight of the polyfluorene. Amino acid, adding 30 parts by weight of compound (Ina -1), and 20 parts by weight of HEA was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole solution 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 10]

The polyglycine solution (PA5) having a concentration of 6 wt% prepared in Synthesis Example 5 and the polyglycine solution (PA7) having a concentration of 6 wt% prepared in Synthesis Example 7 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, an alkenyl-substituted nadic ylidene compound, that is, a compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, HEA, are added, respectively, wherein the polymer is present per 100 parts by weight of the polyfluorene. Amino acid, 20 parts by weight of the compound (Ina-1) was added, and 10 parts by weight of HEA was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole solution 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]

In the polyglycine solution (PA8) having a concentration of 6 wt% prepared in Synthesis Example 8, an alkenyl-substituted nadic ylidene compound (Ina-1) and a radical polymerizable unsaturated double were respectively added. The compound of the bond, HEA, was added with 20 parts by weight of the compound (Ina-1) per 100 parts by weight of the polyglycolic acid, and 10 parts by weight of HEA was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole solution 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. Pieces.

[Comparative Example 1]

The polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA2) having a concentration of 6 wt% prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. . Next, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, followed by dilution to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. 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 polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and the polyglycine solution (PA2) having a concentration of 6 wt% prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. . Next, in the obtained mixture, MHA having a radical polymerizable unsaturated double bond, that is, MHA, was added in a ratio of 10 parts by weight per 100 parts by weight of the polyaminic acid. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture to carry out dilution to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. 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]

In a polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a polyglycine concentration of 4 Wt% 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]

In the polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4, an alkenyl group was substituted with Nadickia at a ratio of 10 parts by weight per 100 parts by weight of the polyglycolic acid. The amine compound is a compound (Ina-1). Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture to carry out dilution to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Test Example 1 to Test Example 15] (Evaluation of Electrical Characteristics)

The liquid crystal display elements produced in Examples 1 to 11 and Comparative Examples 1 to 4 were measured for ion density (long-term reliability of electrical characteristics), and residual DC was measured using a flicker free method. as follows.

1) Determination of ion density

The ion density was measured using a liquid crystal property evaluation device 6254 manufactured by Toyo Technica. The unit of measurement is pico coulomb (pC). The measurement conditions were as follows: the waveform was a triangular wave, the frequency was 0.01 Hz, the voltage was ±10 V, and the measurement temperature was set to 60 °C. The smaller the measured value, the better the electrical characteristics can be said. The results are shown in Table 2.

2) Determination of retention characteristics of ion density

The ion density of the liquid crystal display element produced was determined over time, and the retention characteristics of the ion density were evaluated. The test method for maintaining characteristics is to adopt a method in which a liquid crystal display element is placed in an environment at a temperature of 60 ° C, and a liquid crystal display element is taken out over time during the standing and the ion density is measured. ion The smaller the increase in density (for example, if the increase in ion density after 500 hours of standing under the conditions is 100 pC or less), it can be said that the retention property of the ion density is better, and it can be said that electricity The longer the reliability of the characteristics, the better. The data after 245 hours and 500 hours were shown in Table 2.

3) Residual DC measurement using the flicker free method

Using a FG-110 manufactured by Yokogawa Electric Co., Ltd., a DC voltage of 3 V was superimposed on a rectangular wave of 30 Hz and 1.64 V, and applied for 30 minutes. The flicker elimination voltage was measured for 30 minutes from the end of the application. The table shows the flicker elimination voltage 5 minutes after the end of application. In addition, the measurement temperature was set to 25 °C. The closer the measured value is to 0, the better the electrical characteristics are. The results are shown in Table 2.

As shown in Table 2, when a liquid crystal alignment agent is prepared by mixing a modified agent obtained by combining an alkenyl-substituted nadicylimine compound and a compound having a radical polymerizable unsaturated double bond in polyamic acid, The liquid crystal display element of the liquid crystal alignment film obtained by the liquid crystal alignment agent can suppress the effect of increasing the ion density with time, and the afterimage characteristics are also remarkably improved.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (22)

A liquid crystal alignment agent which is a composition containing an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline or a derivative thereof, wherein the liquid crystal alignment agent is characterized in that The alkenyl-substituted nadic ylidene compound is a compound represented by the formula (Ina), and the ratio of the alkenyl-substituted nadic ylidene compound is 0.01 to 1.00 by weight relative to the polyglycine or a derivative thereof. The ratio of the compound having a radical polymerizable unsaturated double bond is 0.01 to 1.00 by weight based on the weight of the polyglycine or a derivative thereof, and the ratio of the polyaminic acid or a derivative thereof is in the composition Medium is 0.5% by weight to 30% by weight: Wherein, L ¹ and L ² are each independently 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, and a carbon number of 6 to 12; Aryl or benzyl; n is 1 or 2; when n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a cycloalkyl group having 5 to 8 carbon atoms. An aryl group having 6 to 12 carbon atoms, a benzyl group, and a group represented by -Z ¹ -(O) _q -(Z ² O) _r -Z ³ -H, in which Z ¹ and Z are ² and Z ^{3 are} independently an alkylene group having 2 to 6 carbon atoms, q is 0 or 1, and r is an integer of 1 to 30, and a group represented by -(Z ⁴ ) _s -BZ ⁵ -H (this In the group, Z ⁴ and Z ^{5 are} independently an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms, B is a phenylene group, and s is 0 or 1), or a group represented by -BTBH, in which B is a phenylene group, and T is -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- or -SO ₂ -, 1 to 3 hydrogens in W may be substituted by a hydroxyl group; when n = 2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, An arylene group having 6 to 12 carbon atoms, a group represented by -Z ¹ -(O) _q -(Z ² O) _r -Z ³ -, Z ¹ to Z ³ , q and in the group r As described above, in order to _{^{- (Z 4) s -BZ 5}} - represents a group, Z is the group ^4, the meaning of Z ^5, B and s, as described above, or a group represented by at -BTB- The meaning of B and T in the group is as described above, and one to three hydrogens in the W may be substituted with a hydroxyl group. The liquid crystal alignment agent according to claim 1, wherein the liquid crystal alignment agent is an alkenyl-substituted nadicilide compound, poly-proline or a derivative thereof, and a radical polymerizable unsaturated double The composition of the compound of the bond, and the alkenyl-substituted nadicilide compound is at least one of the compounds represented by the formula (Ina-1) to (Ina-3): . The liquid crystal alignment agent according to claim 1 or 2, wherein the liquid crystal alignment agent is a compound containing an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and a poly A composition of a proline or a derivative thereof, and a compound having a radical polymerizable unsaturated double bond is an acrylic acid derivative or a methacrylic acid derivative. The liquid crystal alignment agent according to claim 1 or 2, wherein the liquid crystal alignment agent is a compound containing an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and a poly A composition of a proline or a derivative thereof, and a compound having a radically polymerizable unsaturated double bond is a compound having two or more radically polymerizable unsaturated double bonds, or a mixture containing the same . The liquid crystal alignment agent according to claim 4, wherein the liquid crystal alignment agent is a compound containing an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline or a composition of a derivative thereof, and a compound having a radically polymerizable unsaturated double bond is selected from the group consisting of N,N'-methylenebisacrylamide, N,N'-dihydroxyethylidene-bisacrylamide At least one of ethylene diacrylate and 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline). The liquid crystal alignment agent according to the first aspect of the invention, wherein the polyamic acid is a fragrance represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting at least one of a group of tetracarboxylic dianhydrides with a diamine, and the diamine is selected from the group consisting of non-side chain type diamines represented by formulas (I) to (VII) At least one: H ₂ NX ¹ -NH ₂ (I) Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be subjected to -F, -CH ₃ or -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ , benzyl or hydroxybenzyl. The liquid crystal alignment agent according to claim 1, wherein the polyproline is a polymer obtained by reacting an aromatic tetracarboxylic dianhydride represented by the formula (1) with a diamine, and the second The amine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula (V). -33) and at least one of the non-side chain type diamines represented by the formula (VII-2): The liquid crystal alignment agent according to the first aspect of the invention, wherein the polyamic acid is a fragrance represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting a mixture of at least one of a tetracarboxylic dianhydride and a tetracarboxylic dianhydride other than an aromatic compound with a diamine, and the diamine is selected from the group consisting of formula (I) to formula (VII) At least one of the groups of non-side chain diamines represented: H ₂ NX ¹ -NH ₂ (I) Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be subjected to -F, -CH ₃ or -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ , benzyl or hydroxybenzyl. The liquid crystal alignment agent according to claim 8, wherein the tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), and a formula (35) to a formula (37). At least one of the compounds represented by the formula (39), the formula (44), and the formula (49): The liquid crystal alignment agent according to claim 1, wherein the polyproline is a mixture of the aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic dianhydride other than the aromatic compound and the diamine. a polymer obtained by the reaction, and the diamine is selected from the group consisting of the formula (IV-1), the formula (IV-2), the formula (IV-15), the formula (IV-16), and the formula (V-1). At least one of the non-side chain type diamine represented by the formula (V-12), the formula (V-33), and the formula (VII-2): The liquid crystal alignment agent according to claim 10, wherein the tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), and a formula (35) to a formula (37). At least one of the compounds represented by the formula (39), the formula (44), and the formula (49): The liquid crystal alignment agent according to claim 10, wherein the tetracarboxylic dianhydride other than the aromatic compound is a compound represented by the formula (19): The liquid crystal alignment agent according to the first aspect of the invention, wherein the polyamic acid is a fragrance represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting at least one of a group of tetracarboxylic dianhydrides with a diamine, and the diamine is a mixture of at least one non-side chain type diamine and at least one side chain type diamine, wherein the non-side The chain type diamine is selected from the group consisting of a non-side chain type diamine represented by the formula (I) to the formula (VII), and the side chain type diamine has an alkyl group selected from a carbon number of 3 or more, An alkoxy group having 3 or more carbon atoms, an alkoxyalkyl group having 3 or more carbon atoms, a group having a steroid skeleton, and an alkyl group having a carbon number of 1 or more and a carbon number at the terminal a side chain group in the group of a ring having 1 or more alkoxy groups or an alkoxyalkyl group having 2 or more carbon atoms: H ₂ NX ¹ -NH ₂ (I) Wherein X ¹ is a linear alkylene group having 2 to 12 carbon atoms; X ² is a linear alkylene group having 1 to 12 carbon atoms; and X ^{3 is} independently a single bond, -O-, -CO-, - CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _t -O-, -S-, -SS-, -SO ₂ -, -S-(CH ₂ ) _t -S- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be subjected to -F, -CH ₃ or -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ , benzyl or hydroxybenzyl. The liquid crystal alignment agent according to claim 13, wherein the side chain type diamine is a diamine selected from the group consisting of compounds represented by formula (VIII) to formula (XII): Wherein R ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O- or an alkylene group having a carbon number of 1 to 6 And any -CH ₂ - in the alkylene group may be substituted by -O-, -CH=CH- or -C≡C-; R ² is a group having a steroid skeleton, and the carbon number is 3 to 30 An alkyl group, a phenyl group having a carbon number of 3 to 30 or an alkoxy group having 3 to 30 carbon atoms as a substituent, or a group represented by the formula (D-1), and wherein the alkyl group is Any -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-; Wherein R ¹³ , R ¹⁴ and R ^{15 are} independently a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxygen having 1 to 3 carbon atoms. An alkylene group or an alkyleneoxy group having a carbon number of 1 to 3; a ring B and a ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R ¹⁶ and R ^{17 are} independently a fluorine or a group a group, and m1 and m2 are independently 0, 1, or 2; e, f, and g are independently an integer of 0 to 3, and their total value is 1 or more; R ¹⁸ is an alkyl group having 1 to 30 carbon atoms. An alkoxy group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. Any of these alkyl groups, alkoxy groups and alkoxyalkyl groups may be substituted by fluorine, and optionally CH ₂ - may be substituted with a difluoromethylene group or a group represented by the formula (D-2); Wherein R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are} independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is an integer of 1 to 100; Wherein R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or - CH ₂ -; Wherein R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or -CH ₂ -; and R ⁶ and R ^{7 are} independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group; Wherein R ⁸ is an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-; R ^{9 is} independently -O - or an alkylene group having a carbon number of 1 to 6; ring A is a 1,4-phenylene group or a 1,4-cyclohexylene group; a is 0 or 1; b is 0, 1 or 2; and, c is independent Is 0 or 1; Wherein R ¹⁰ is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms; and R ¹¹ is hydrogen, an alkyl group having 1 to 30 carbon atoms or a fluorine having 1 to 30 carbon atoms; Alkyl; R ^{12 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; and d is independently 0 or 1. The liquid crystal alignment agent according to claim 13, wherein the side chain type diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4), formula (VIII-5), and formula (VIII-6). , a diamine in the compound represented by the formula (XI-2) and the formula (XI-4): Wherein R ²³ and R ^{24 are} independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms; and R ²⁹ and R ^{30 are} independently an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30 alkoxy groups. The liquid crystal alignment agent according to claim 13, wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), and formula (IV-). 16) a diamine in the compound represented by the formula (V-1) to the formula (V-12), the formula (V-33), and the formula (VII-2), wherein the side chain type diamine is selected from the formula (VIII) -2) a diamine in the compound represented by the formula (VIII-4), the formula (VIII-5), the formula (VIII-6), the formula (XI-2) and the formula (XI-4): Wherein R ²³ and R ^{24 are} independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms; and R ²⁹ and R ^{30 are} independently an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30 alkoxy groups. The liquid crystal alignment agent according to claim 1, wherein the polyproline is selected from the group consisting of at least one of a mixture of at least one aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride. a polymer obtained by reacting a non-side chain type diamine, and a mixture obtained by reacting a mixture of the tetracarboxylic dianhydride with at least one side chain type diamine and at least one of the non-side chain type diamines At least one of the polymers, wherein the aromatic tetracarboxylic dianhydride is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14), other than the aromatic The tetracarboxylic dianhydride is represented by the formula (19), the formula (23), the formula (25), the formula (35) to the formula (37), the formula (39), the formula (44), and the formula (49). The non-side chain type diamine is of the formula (IV-1), the formula (IV-2), the formula (IV-15), the formula (IV-16), the formula (V-1) to the formula (V-12). The formula (V-33) and the formula (VII-2) indicate that the side chain type diamine is a formula (VIII-2), a formula (VIII-4), a formula (VIII-5), and a formula (VIII-). 6), formula (XI-2) and formula (XI-4); Wherein R ²³ and R ^{24 are} independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms; and R ²⁹ and R ^{30 are} independently an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30 alkoxy groups. The liquid crystal alignment agent according to claim 17, wherein the polyproline is a mixture of at least one aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride and at least one non-side A polymer obtained by reacting a chain diamine. The liquid crystal alignment agent according to claim 17, wherein the polyproline is obtained by at least one aromatic tetracarboxylic dianhydride and at least one a polymer obtained by reacting a mixture of tetracarboxylic dianhydrides other than aromatic with at least one non-side chain type diamine, and at least one non-side chain type diamine and at least one mixture of the tetracarboxylic dianhydride A mixture of polymers obtained by reacting a mixture of side chain type diamines. The liquid crystal alignment agent according to claim 17, wherein the polyproline is at least one selected from the group consisting of at least one aromatic tetracarboxylic dianhydride and at least one aromatic A mixture of tetracarboxylic dianhydrides other than the group is obtained by reacting a mixture of at least one non-side chain type diamine and at least one side chain type diamine. A liquid crystal alignment film which is formed by coating a liquid crystal alignment agent according to item 1 of the above patent application on a substrate and firing it in a state of a film. A liquid crystal display device having a pair of substrates disposed opposite to each other, an electrode formed on one or both of opposing surfaces of the pair of substrates, and opposing faces of the pair of substrates And a liquid crystal alignment layer formed on the liquid crystal alignment layer, wherein the liquid crystal alignment film is a liquid crystal alignment film according to claim 21 of the patent application.