TWI492966B - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display - Google Patents

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, the liquid crystal alignment agent containing a diamine having a piperazine in a main chain (diamine) Polyamic acid obtained by reacting with tetracarboxylic dianhydride or a derivative thereof.

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

Various components are known in the liquid crystal display element, and the technical development of the liquid crystal display element is realized not only by the driving method of the liquid crystal display element or the structure of the liquid crystal display element, but also by the composition used for the liquid crystal display element. The components are improved to achieve. Generally, a liquid crystal display element has a liquid crystal alignment film for aligning a liquid crystal composition in a liquid crystal layer in a specific direction. The liquid crystal alignment film is an important element related to the display quality of the liquid crystal display element, and the action of the liquid crystal alignment film becomes important year by year as the quality of the liquid crystal display element is improved.

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, film formation is performed by a method such as heating to form a liquid crystal alignment film.

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, for example, even if the initial ion density is low, the ion density (long-term reliability) after the high-temperature acceleration test is increased.

Attempts have been made to solve the problems described. For example, a polylysine composition for forming a liquid crystal alignment film and combining two or more kinds of polylysine having different physical properties (for example, reference to Japan) is known. Patent Publication No. Hei 11-193345 and Japanese Patent Laid-Open No. Hei 11-193347.

On the other hand, a liquid crystal alignment agent for forming a film having a high yield of oxime iodization even at a low temperature is known as a liquid crystal alignment agent containing a reaction of a diamine with a tetracarboxylic dianhydride. In the case of the obtained polyamine, the diamine has a divalent organic group containing a basic nitrogen atom such as a pyridazine (for example, refer to Japanese Laid-Open Patent Publication No. Hei 9-194725).

Further, a polylysine obtained by reacting an aromatic diamine having a pyridazine with a tetracarboxylic dianhydride and its thermal properties are known (for example, refer to Journal of Polymer Science: Part A: Polymer Chemistry, vol. 30, P1099-1102 (1992)).

In these prior art, there is still room for further research on the liquid crystal alignment agent which forms the liquid crystal alignment film of the present invention which is required to be further improved, in terms of electrical characteristics of the obtained liquid crystal alignment film or materials for obtaining desired electrical characteristics.

The present invention provides a liquid crystal display element exhibiting a desired ion density and achieving long-term stability of the ion density, a liquid crystal alignment exhibiting a desired ion density in the liquid crystal display element, and long-term stability of the ion density. A film, and a liquid crystal alignment agent capable of forming the liquid crystal alignment film.

The present inventors have found that a composition containing polyaminic acid or a derivative thereof containing an aromatic diamine having a pyridazine as a raw material can be used for a liquid crystal alignment agent, and can have a liquid crystal having a liquid crystal alignment film formed thereby. The display element imparts good ion density and long-term reliability, thereby completing the present invention.

The present invention includes the following constitutions.

[1] A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent being characterized by:

The diamine contains a diamine represented by the following formula (N).

In the formula (N), A ¹ independently represents a monovalent organic group, A ² independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4.

[2] The liquid crystal alignment agent according to [1], wherein A ^{1 is} independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, acetaminophen, fluorine, or the like. Chlorine or bromine, A ^{2 is} independently an alkyl group having 1 to 3 carbon atoms.

[3] The liquid crystal alignment agent according to [1] or [2], wherein the diamine represented by the formula (N) has an amino group at a p-position in a phenyl group at both ends.

[4] The liquid crystal alignment agent according to any one of [1] to [3], wherein the diamine represented by the formula (N) is selected from the group consisting of the following structural formula (N)-1; Formula (N)-2, Structural Formula (N)-5 to Structural Formula (N)-7, Structural Formula (N)-9, Structural Formula (N)-10, Structural Formula (N)-14, Structural Formula ( N)-17, a structural formula (N)-18, a structural formula (N)-21 to a structural formula (N)-23, a structural formula (N)-26, and a compound represented by the structural formula (N)-28 One or more of the ethnic groups.

[5] The liquid crystal alignment agent according to [4], wherein the diamine represented by the formula (N) is a compound represented by the structural formula (N)-1 and the structural formula (N)-2 One or both of them.

[6] The liquid crystal alignment agent according to any one of [1] to [5] wherein the diamine further comprises the following general formula (VIII) and the general formula (X) to the general formula (XIII). a diamine having a side chain structure.

In the formula (VIII), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m - (m represents an integer of 1 to 6), R ¹ represents a group having a steroid skeleton and a group represented by the following formula (IX). When the positional relationship of two amino groups bonded to the benzene ring is para, R ¹ further contains a carbon number. When the positional relationship is a meta position, R ¹ further includes an alkyl group having 1 to 30 carbon atoms or a phenyl group, and any -CH ₂ - in the alkyl group may independently pass through - CF ₂ -, -CHF-, -O- (here non-continuous), -CH=CH- or -C≡C-, -CH ₃ may be via -CH ₂ F, -CHF ₂ or -CF ₃ Substituted, the hydrogen of the phenyl group may be independently substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ .

In the formula (IX), A ⁴ and A ⁵ each independently represent a single bond, -O- (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon number. Is an alkylene group of 1 to 12, and R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl (pyridine-2,5-diyl), naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl (anthracene-9, 10-diyl), R ⁴ represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b respectively represent integers of 0 to 4, c, d and e represent integers of 0 to 3, respectively, and f and g each independently represent an integer of 0 to 2, And c+d+e≧1.

In the general formulae (X) and (XI), R ⁵ independently represents -H or -CH ₃ , R ⁶ represents -H or an alkyl or alkenyl group having 1 to 20 carbon atoms, and A ⁶ independently represents a single bond, -C(=O)- or -CH ₂ -, in the formula (XI), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group.

In the general formulae (XII) and (XIII), A ⁷ independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and in the formula (XII), R ⁹ represents -H or a carbon number of 1 to 30. An alkyl group in which any -CH ₂ - of an alkyl group having 2 to 30 carbon atoms may be subjected to -O- (here, discontinuous), -CH=CH- or -C≡C- Substituted, A ⁸ represents a single bond or an alkylene group having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexylene, and h represents 0 or 1, in the formula (XIII) R ¹⁰ represents an alkyl group having 6 to 22 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 22 carbon atoms.

[7] The liquid crystal alignment agent according to [6], wherein the diamine having a side chain structure is selected from the group consisting of the following formula (VIII-2) and formula (VIII-4) to (VIII-6), at least one of the compounds represented by the formula (XII-2), the formula (XII-4), and the formula (XII-6).

In the above formula, R ²³ , R ²⁹ and R ³⁰ each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.

The liquid crystal alignment agent according to any one of [1] to [7] wherein the diamine further comprises the following general formula (I) to general formula (VII) and general formula (XV) a diamine represented by a side chain structure.

In the formula (I), X represents -(CH ₂ ) _m - (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents a single Bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N( CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH ₂ ) _m -S-(m represents an integer of 1 to 6), and in the formula (V), Z represents a single bond or does not exist, and in the formula (XV), R ³³ and R ³⁴ each independently represent a carbon number of 1 to Alkyl or phenyl of ³ , A ³ independently represents a methylene group, a phenylene group or an alkyl substituted phenylene group. 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the general formulae (II) to (VII), a hydrogen bonded to a cyclohexane ring or a benzene ring may be independently substituted with -F, - CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (IV) may be substituted with a benzyl group.

[9] The liquid crystal alignment agent according to [8], wherein the diamine having no side chain structure is selected from the group consisting of the following structural formula (IV-1), structural formula (IV-2), and structure Formula (IV-15) to Structural Formula (IV-17), Structural Formula (V-1) to Structural Formula (V-12), Structural Formula (V-33), Structural Formula (V-35) to Structural Formula ( At least one of a compound represented by V-37), Structural Formula (VII-2), and Structural Formula (XV-1).

[10] The liquid crystal alignment agent according to any one of [1] to [9] wherein the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride.

[11] The liquid crystal alignment agent according to [10], wherein the aromatic tetracarboxylic dianhydride is represented by the following structural formula (1), structural formula (2), and structural formula (5) to structural formula. (7) and at least one of the compounds represented by the formula (14).

[12] The liquid crystal alignment agent according to [11], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the structural formula (1).

[13] The liquid crystal alignment agent according to any one of [1] to [12] wherein the tetracarboxylic dianhydride comprises an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. One or both of them.

[14] The liquid crystal alignment agent according to [13], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (19), structural formula (23) At least one of the compounds represented by the structural formula (25), the structural formula (35) to the structural formula (39), the structural formula (44), and the structural formula (49).

[15] The liquid crystal alignment agent according to [14], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the structural formula (19), structural formula (23) At least one of the compounds represented by the structural formula (37) and the structural formula (49).

[16] The liquid crystal alignment agent according to any one of [6], wherein the liquid crystal alignment agent contains the polyamic acid or derivatives A and B thereof, and the polyfluorene The amine acid or derivative A thereof comprises the diamine having a side chain structure in the diamine, and one or both of the polyamine or a derivative thereof and a diamine of B are included A diamine represented by the formula (N).

The liquid crystal alignment agent according to any one of [1] to [16] wherein the liquid crystal alignment agent further contains an alkenyl-substituted nadic quinone imine compound and has a radical. One or more of a compound having a polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound.

[18] The liquid crystal alignment agent according to [17], wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5- Ethene-2,3-dimethylimine)phenyl}methane (bis{4-(allylbicyclo[2.2.1] ept-5-ene-2,3-dicarboxyimide)phenyl}methane), N,N'- M-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine) and N,N'-hexamethylene-bis(allylbicyclo[ 2.2.1] One or more of the group consisting of hept-5-ene-2,3-dimethylimine.

[19] The liquid crystal alignment agent according to [18], wherein the alkenyl-substituted nadicilide compound is bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)phenyl}methane.

[20] The liquid crystal alignment agent according to [17], wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-methylenebis acrylamide (N, N) '-methylene bisacrylamide), N,N'-dihydroxyethylene bisacrylamide, ethylene bisacrylate, and 4,4'-methylene double ( One or more of the groups consisting of 4,4'-methylene bis(N,N-dihydroxyethylene acrylate aniline).

[21] The liquid crystal alignment agent according to [20], wherein the compound having a radical polymerizable unsaturated double bond is N,N'-dihydroxyethylenebisacrylamide.

[22] The liquid crystal alignment agent according to [17], wherein the oxazine compound is selected from the group consisting of the following formula (b-1), formula (c-1), formula (c-3), and (c-5), formula (c-7), formula (c-9), formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula ( F-2) One or more of the group consisting of the compounds represented by the formula (f-4).

[23] The liquid crystal alignment agent according to [22], wherein the oxazine compound is a compound represented by the formula (c-1).

[24] The liquid crystal alignment agent according to [17], wherein the oxazoline compound is 2,2'-bis(2-oxazoline) and 1,3-double (4,5-di One or both of 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

[25] The liquid crystal alignment agent according to [24], wherein the oxazoline compound is 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

[26] The liquid crystal alignment agent according to [17], wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine (N, N) , N', N'-tetraglycidyl-m-xylenediamine), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl -4,4'-diaminodiphenylmethane, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2 ,3-glycidyloxy]phenyl)]ethyl]phenyl]propane (2-[4-(2,3-epoxy propoxy)phenyl]-2-[4-[1,1-bis[4 -([2,3-epoxy propoxy]phenyl)]ethyl]henyl]ropane), 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (3, 4-epoxy cyclohexenyl methyl-3', 4'-epoxy cyclohexene carboxylate), N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3, One or more of the group consisting of 2-(3,4-epoxy cyclohexyl)ethyl trimethoxy silane.

[27] The liquid crystal alignment agent according to [26], wherein the epoxy compound is 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylic acid Ester or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

[28] A liquid crystal alignment film formed by heating a coating film of the liquid crystal alignment agent according to any one of [1] to [27].

[29] A liquid crystal display element having a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and an alignment of the liquid crystal molecules in a predetermined direction A liquid crystal alignment film characterized in that the liquid crystal alignment film is the liquid crystal alignment film according to [28].

[Effect of the invention]

According to the present invention, it is possible to provide a liquid crystal display element which has a high ion density and is excellent in long-term reliability corresponding to the change in the ion density with time, and can be applied to various driving methods.

The above described features and advantages of the present invention will be more apparent from the following description.

The liquid crystal alignment agent of the present invention contains polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine. The poly-proline derivative is a component which is dissolved in a solvent when it is prepared as a liquid crystal alignment agent which will be described later, and can be formed into a polysiloxane when the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later. A component of a liquid crystal alignment film having an amine as a main component. Examples of such a derivative of polylysine include soluble polyimine, polyphthalate, and polyamidamine, and more specifically, 1) all amino and carboxyl groups of polyglycine Polyimine which is obtained by dehydration ring closure reaction, 2) partial polyimine which is partially subjected to dehydration ring closure reaction, 3) polyphthalate which converts carboxyl group of polylysine into ester, 4 a poly-proline-polyamine copolymer obtained by replacing a part of an acid dianhydride contained in a tetracarboxylic dianhydride compound with an organic dicarboxylic acid, and further, 5) making the poly-proline A polyamidoquinone imine obtained by subjecting a part or all of the polyamidamide copolymer to a dehydration ring-closure reaction. The polyamic acid or a derivative thereof may be one compound or two or more compounds.

The diamine contains a diamine represented by the following formula (N). The diamine used in the present invention may be one compound or two or more compounds.

In the formula (N), A ¹ independently represents a monovalent organic group, A ² independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. Further, in the present invention, halogen is included in the organic group.

The A ¹ and A ² may each use various monovalent organic groups. A ¹ is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, acetamide, fluorine, chlorine or bromine. A ² is preferably an alkyl group independently having 1 to 3 carbon atoms.

The diamine represented by the formula (N) has an amino group at each of the phenyl groups at both ends. The positions of these amino groups can be independently at any of the ortho, meta and para positions relative to the pyridazine. From the viewpoint that the production of the diamine is relatively easy, the positions of these amino groups are preferably all para-position.

In the present invention, examples of the diamine represented by the formula (N) include the following compounds.

The diamine represented by the above formula (N) is preferably represented by the structural formula (N)-1, structural formula (N)-2, structural formula (N)-5 to structural formula (N)-7, structural formula. (N)-9, structural formula (N)-10, structural formula (N)-14, structural formula (N)-17, structural formula (N)-18, structural formula (N)-21-structure formula (N And a compound represented by the structural formula (N)-26 and the structural formula (N)-28, and a compound represented by the structural formula (N)-1 and the structural formula (N)-2 is more preferable.

The diamine represented by the above formula (N) is agglomerated in the liquid crystal alignment agent of the present invention from the viewpoint of exhibiting a desired ion density in the liquid crystal display element and exhibiting long-term stability of the ion density. The diamine of the proline is preferably contained in an amount of from 20% to 100%, more preferably from 35% to 100%, in terms of a molar ratio.

The diamine represented by the above formula (N) can be produced by a known method. For example, as described in JP-A-52-14780, it is possible to have a corresponding substituent under ordinary reducing conditions using a reducing agent such as tin or hydrochloric acid. The nitro group of the compound obtained by subjecting Nitrobenzene or a derivative thereof to a pyridine reaction is reduced to an amino group.

The diamine may contain only the diamine represented by the above formula (N), and may further contain other diamines. Examples of the other diamine include a diamine having a side chain structure and a diamine having no side chain structure. Such other diamines may be one compound or two or more compounds.

The diamine having a side chain structure means a diamine having a substituent (side chain) which branches autonomously when a substituent linking two amino groups is used as a main chain, and can exhibit desired Pretilt angl. The side chain in the diamine having a side chain structure may be appropriately selected according to the required pretilt angle. For example, the side chain may be a group having a carbon number of 3 or more. Examples of the diamine having a side chain structure include compounds represented by the following formula (VIII) and formula (X) to formula (XIII).

In the formula (VIII), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m - (m represents an integer of 1 to 6), R ¹ represents a group having a steroid skeleton, a group represented by the following formula (IX), and when the positional relationship of the two amino groups bonded to the benzene ring is para, R ¹ further contains a carbon number of In the alkyl group of 1 to 30, when the positional relationship is meta, R ¹ further contains an alkyl group having 1 to 30 carbon atoms or a phenyl group. In the alkyl group, any -CH ₂ - may be independently substituted by -CF ₂ -, -CHF-, -O- (here, discontinuous), -CH=CH- or -C≡C-, - CH ₃ may be substituted with -CH ₂ F, -CHF ₂ or -CF ₃ . Moreover, the hydrogen of the phenyl group may be independently substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ .

In the formula (IX), A ⁴ and A ⁵ each independently represent a single bond, -O- (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon number. Is an alkylene group of 1 to 12, and R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or oxime-9 , 10-diyl, R ⁴ represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or -CN -OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b respectively represent integers of 0 to 4, c, d and e represent integers of 0 to 3, respectively, and f and g each independently represent an integer of 0 to 2 And c+d+e≧1.

In the general formulae (X) and (XI), R ⁵ independently represents -H or -CH ₃ , R ⁶ represents -H or an alkyl or alkenyl group having 1 to 20 carbon atoms, and A ⁶ independently represents a single bond, -C(=O)- or -CH ₂ -. Further, in the formula (XI), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group.

In the general formulae (XII) and (XIII), A ⁷ independently represents -O- or an alkylene group having 1 to 6 carbon atoms. Further, in the formula (XII), R ⁹ represents -H or an alkyl group having 1 to 30 carbon atoms, and in the alkyl group, any -CH ₂ - of the alkyl group having 2 to 30 carbon atoms may be subjected to -O- (here is discontinuous), -CH=CH- or -C≡C- is substituted, A ⁸ represents a single bond or an alkylene group having 1 to 3 carbon atoms, and ring T represents 1,4-phenylene group or 1,4-cyclohexylene, h represents 0 or 1. Further, in the formula (XIII), R ¹⁰ represents an alkyl group having 6 to 22 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 22 carbon atoms.

Examples of the diamine represented by the formula (VIII) include the following formula (VIII-1) to formula (VIII-37) and two groups represented by the structural formula (VIII-38) to the structural formula (VIII-43). amine.

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

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

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

Among these diamines, a diamine represented by the formula (VIII-1) to the formula (VIII-11) is preferred, and a formula (VIII-2) and a formula (VIII-4) to a formula (VIII) are more preferred. -6) The diamine represented.

The diamine represented by the above formula (X) is preferably one of two "NH ₂ -Ph-A ⁶ -O-" in the formula (X) bonded to the 3-position of the steroid skeleton, One is bonded to 6 digits. Further, the two amino groups are bonded to the benzene ring carbon, respectively, and are preferably bonded to the meta or para position with respect to the bonding position of A ⁶ .

The diamine represented by the formula (X) is, for example, a diamine represented by the following structural formula (X-1) to structural formula (X-4).

In the diamine represented by the above formula (XI), in the formula (XI), two "NH ₂ -(R ⁶ -)Ph-A ⁶ -O-" are bonded to the carbon of the benzene ring, respectively. It is preferred to bond to the meta or para carbon with respect to the carbon to which the steroid skeleton is bonded. Further, the two amino groups are bonded to the carbon of the benzene ring, respectively, and are preferably bonded to the meta or para position with respect to A ⁶ .

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

In the diamine represented by the above formula (XII), in the formula (XII), two amino groups are bonded to the carbon of the benzene ring, respectively, preferably bonded to the meta or para position relative to A ⁷ . on.

The diamine represented by the formula (XII) is, for example, a diamine represented by the following formula (XII-1) to formula (XII-8).

In the general formulae (XII-1) to (XII-3), R ²⁹ preferably represents -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably It is an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. Further, in the general formulae (XII-4) to (XII-8), R ³⁰ preferably represents -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably Preferably, it is an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms.

In the diamine represented by the above formula (XIII), in the formula (XIII), two amino groups are bonded to the carbon of the benzene ring, respectively, preferably bonded to the meta or para position relative to A ⁷ . on.

The diamine represented by the formula (XIII) is, for example, a diamine represented by the following formula (XIII-1) to (XIII-3).

In the general formulae (XIII-1) to (XIII-3), R ³¹ preferably represents an alkyl group having 6 to 22 carbon atoms, and more preferably an alkyl group having 6 to 20 carbon atoms. R ³² is preferably an alkyl group having -H or a carbon number of 1 to 22, and more preferably an alkyl group having 1 to 10 carbon atoms.

The diamine having a side chain structure is preferably selected from the group consisting of the general formula (VIII-2), the general formula (VIII-4) to the general formula (VIII-6), the general formula (XII-2), and the general formula ( XII-4) and at least one of the compounds represented by the formula (XII-6).

From the viewpoint of exhibiting a desired pretilt angle in the liquid crystal display element, the diamine having a side chain structure is preferably selected from a molar ratio of a polyamine of a polylysine constituting the liquid crystal alignment agent of the present invention. It is contained in an amount of 1% to 90%, more preferably 5% to 70%.

The diamine having no side chain structure means a diamine having no substituent (side chain) which branches autonomously when a substituent linking an amino group is used as a main chain, and can exhibit a desired Pretilt angle. Examples of the diamine having no side chain structure include compounds represented by the following formula (I) to formula (VII) and formula (XV).

In the formula (I), X represents -(CH ₂ ) _m - (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents a single Bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N( CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH ₂ ) _m -S-(m represents an integer of 1 to 6), and in the formula (V), Z represents a single bond or does not exist, and in the formula (XV), R ³³ and R ³⁴ each independently represent a carbon number of 1 to Alkyl or phenyl of ³ , A ³ independently represents a methylene group, a phenylene group or an alkyl substituted phenylene group. 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the general formulae (II) to (VII), a hydrogen bonded to a cyclohexane ring or a benzene ring may be independently substituted with -F, - CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (IV) may be substituted with a benzyl group.

The diamine represented by the formula (I) is, for example, a diamine represented by the following structural formula (I-1) to structural formula (I-3).

The diamine represented by the formula (II) is, for example, a diamine represented by the following structural formula (II-1) or structural formula (II-2).

The diamine represented by the formula (III) is, for example, a diamine represented by the following structural formula (III-1) to structural formula (III-3).

The diamine represented by the formula (IV) is, for example, a diamine represented by the following structural formula (IV-1) to structural formula (IV-17).

The diamine represented by the formula (V) is, for example, a diamine represented by the following structural formula (V-1) to structural formula (V-37).

The diamine represented by the formula (VI) is, for example, a diamine represented by the following structural formula (VI-1) to structural formula (VI-6).

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

The diamine represented by the formula (XV) is, for example, a compound represented by the following structural formula (XV-1).

Among these diamines, the diamine having no side chain structure preferably has a structural formula (IV-1) to a structural formula (IV-5), a structural formula (IV-15) to a structural formula (IV-17), and a structure. Formula (V-1) to Structural Formula (V-12), Structural Formula (V-26), Structural Formula (V-27), Structural Formula (V-31), Structural Formula (V-33), Structural Formula ( V-35) to structural formula (V-37), structural formula (VI-1), structural formula (VI-2), structural formula (VI-6), structural formula (VII-1) to structural formula (VII- 5) and the diamine represented by the structural formula (XV-1), more preferably, the structural formula (IV-1), the structural formula (IV-2), the structural formula (IV-15) to the structural formula (IV-17), Structural formula (V-1) to structural formula (V-12), structural formula (V-33), structural formula (V-35) to structural formula (V-37), structural formula (VII-2), and structural formula The diamine represented by (XV-1).

The diamine having no side chain structure is a diamine of a poly-proline which constitutes the liquid crystal alignment agent of the present invention, from the viewpoint of exhibiting an electric property required for an ion density or the like in the liquid crystal display element. The ear ratio meter preferably contains from 1% to 98%, more preferably from 10% to 95%.

The diamine other than the diamine represented by the general formula (I) to the general formula (VIII) and the general formula (X) to the general formula (XIII) can be used as the diamine in the present invention. Examples of such other diamines include naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, and diamines having a side chain structure other than the general formulae (VIII) to (XII).

Examples of the other diamines include compounds represented by the following general formulae (1') to (8').

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

In the diamine constituting the polyproline in the liquid crystal alignment agent of the present invention, the other diamine can be used within the range not to the extent that the effects of the present invention are impaired.

For the diamine, a part of the diamine may be replaced with a monoamine in a range of 40 mol% or 40 mol% or less of the monoamine to the diamine in each diamine. Such substitution can cause termination of the polymerization reaction in the formation of poly-proline, so that the polymerization can be further inhibited. Therefore, by such substitution, the molecular weight of the obtained polymer (polylysine or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-decylamine. , n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine and n-dodecylamine.

The tetracarboxylic dianhydride used in the present invention may be one compound or two or more compounds. Examples of the tetracarboxylic acid include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride.

The aromatic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride obtained by bonding two carboxyl groups bonded to the aromatic compound. Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following structural formulae (1) to (18).

The aromatic tetracarboxylic dianhydride is preferably a compound represented by the structural formula (1), the structural formula (2), the structural formula (5) to the structural formula (7), and the structural formula (14), and more preferably The compound represented by the structural formula (1).

The alicyclic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride obtained by bonding two carboxyl groups bonded to the alicyclic compound. Examples of the alicyclic tetracarboxylic dianhydride include the following structural formulae (19) to (22), structural formulas (24) to (44), and structural formulae (49) to (65). The compound represented.

The alicyclic tetracarboxylic dianhydride preferably has the structural formula (19), structural formula (25), structural formula (35) to structural formula (37), structural formula (39), structural formula (44), and The compound represented by the structural formula (49) is more preferably a compound represented by the above structural formula (19), structural formula (37) and structural formula (49).

The aliphatic tetracarboxylic dianhydride is a compound having two acid anhydrides obtained by bonding two carboxyl groups bonded to an aliphatic compound. Examples of the aliphatic tetracarboxylic dianhydride include compounds represented by the following structural formula (23), structural formula (45) to structural formula (48), structural formula (66), and structural formula (67).

The aliphatic tetracarboxylic dianhydride is preferably a compound represented by the structural formula (23).

As the tetracarboxylic dianhydride, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the structural formulae (1) to (67) can be used. Examples of the other tetracarboxylic dianhydride include tetracarboxylic dianhydride having a side chain structure. By using a tetracarboxylic dianhydride having a side chain structure, the pretilt angle of the liquid crystal display element can be increased.

Examples of the tetracarboxylic dianhydride having a side chain structure include compounds having a steroid skeleton represented by the following structural formula (68) and structural formula (69).

The tetracarboxylic dianhydride may be used in any kind and blending amount within the range in which the effects of the present invention are achieved.

It is also possible to replace a part of the tetracarboxylic dianhydride with a carboxylic acid monoanhydride. Such replacement can cause termination of the polymerization reaction when polyamic acid is formed, and further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the obtained polymer (polylysine or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride may be within the range not impairing the effects of the present invention, and the basis thereof is preferably 10 mol% or 10 mol% or less of the total amount of the tetracarboxylic dianhydride. The tetracarboxylic dianhydride which is replaced with a carboxylic anhydride may be one type or two or more types as long as the effect of the present invention is not impaired. Examples of the carboxylic acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, N-hexadecyl succinic anhydride and cyclohexanoic anhydride.

The tetracarboxylic dianhydride may be substituted with a portion of the tetracarboxylic dianhydride to the dicarboxylic acid in a range of 10 mol% or 10 mol% or less of the dicarboxylic acid to the tetracarboxylic dianhydride. The tetracarboxylic dianhydride substituted with a dicarboxylic acid may be one type or two or more types as long as the effects of the present invention are not impaired.

The monomer of the polyamic acid or a derivative thereof may further contain a monoisocyanate compound. By including a monoisocyanate compound in the monomer, the terminal of the obtained polyglycine or a derivative thereof is modified, and the molecular weight is adjusted. By using this terminal-modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From the viewpoint of the above, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid or a derivative thereof may be the same as the well-known polyperglycine or derivative thereof used in the formation of a film of polyimine, in addition to the diamine represented by the general formula (N). Made in the field. The total amount of the tetracarboxylic dianhydride added is preferably about the same as the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

The molecular weight of the polyamic acid or a derivative thereof is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or a derivative thereof can be determined by measurement by a gel permeation chromatography (GPC) method.

For the polyamic acid or a derivative thereof, the solid component obtained by precipitating with a large amount of poor solvent can be confirmed by infrared spectroscopy (IR) or nuclear magnetic resonance (NMR) analysis. . Further, gas chromatography (Gas Chromatography, GC), high-efficiency liquid can be carried out by extracting an extract obtained by extracting an organic solvent of a polylysine or a derivative of a derivative thereof with an aqueous solution of a strong alkali such as KOH or NaOH. The cells used were confirmed by high performance liquid Chromatography (HPLC) or gas chromatography-mass spectrometer (GC-MS) analysis.

The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid or a derivative thereof. The other components may be one type or two or more types.

For example, from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted nadic ylidene imine compound. The alkenyl-substituted nadicylimine compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the alkenyl-substituted nadicylimine compound is preferably from 0.01 to 1.00, more preferably 0.01, based on the weight ratio of the poly-proline or the derivative thereof in the liquid crystal alignment agent. ～0.70, more preferably 0.01 to 0.50.

The alkenyl-substituted nadicylimine compound is preferably a compound which can be dissolved in a solvent which dissolves the poly-proline or the derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadicylimine compound include compounds represented by the following formula (Ina).

In the general formula (Ina), L ¹ and L ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an aromatic group. Base or benzyl, n represents 1 or 2.

When n=1, W represents 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, -Z ¹ -(O) _q -(Z ² O) _r -Z ³ -H (Z ¹ , Z ² and Z ³ independently represent an alkylene group having 2 to 6 carbon atoms, and q represents 0 or 1, and r represents a group represented by an integer of 1 to 30, and -(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ independently represent an alkylene group having 1 to 4 carbon atoms or a carbon number Is a cycloalkylene group of 5-8, B represents a phenylene group, and s represents a group represented by 0 or 1), with -BTBH (B represents a phenylene group, and T represents -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 W 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(ethyleneoxy)ethyl group having 4 to 10 carbon atoms. 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 general formula (Ina), W represents 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 1 -O- (Z 2 O)} r -Z 3 - (Z 1 ~ Z 3 and r meaning as described above) is a group represented to ^{-Z 4 -BZ 5 - (Z 4} , Z 5 and B The meaning of the group as described above, with -B-(OB) _s -T-(BO) _s -B- (B represents a phenylene group, and T represents an alkylene group having a carbon number of 1 to 3, - O- or -SO ₂ -, s represents 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 benzylidene group, a xylylene group, and a -C ₃ H ₆ -O-(Z ² -O) group. _r- OC ₃ H ₆ -(Z ² represents an alkylene group having 2 to 6 carbon atoms, r represents 1 or 2), and -BTB-(B represents a phenylene group, and T represents -CH a group represented by ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (B represents a phenylene group), and 1 or 2 hydrogen groups of these groups a group substituted by a hydroxyl group.

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 0.5 hour 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-dimethylimine (N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboximide), N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, 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-dimethylimine, N-(2-ethylhexyl)-allyl ( Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-methylallyl bicyclo [2.2.1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine , N-cyclohexyl- Propyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine, N-phenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-phenyl-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Yttrium, 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]hept-5-ene-2,3-dimethylhydrazine Imine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2-hydroxyethyl )-Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,2-dimethyl-3-hydroxypropyl)-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2,2-dimethyl-3-hydroxypropyl)-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 (A Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, 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-carboximine, N-(4-hydroxyphenyl)-allyl (A 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-carboximine, N-(3-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2 -(2-hydroxyethoxy)ethyl}-methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5- Alkene-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]hept-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)phenyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Terpenoids, and their oligomers (oligomers);

N,N'-Ethylene-bis(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'-ethylidene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino), N,N'-ethylene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-triam Methyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-hexamethylene-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine), N,N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N, N'-docamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-cyclohexylene-double ( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine)propoxy}ethane, 1,2-bis{3'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine) 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-dimethylimineimine)propoxy}butane, 1,4-double {3'- (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}butane, 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- Alkene-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-carboximine), N,N'-{(1- Methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-p-xylene Base-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-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-dimethylimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) phenoxy }phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}benzene 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-(methylallylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, Double {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine)phenyl}ether, {4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine)phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}anthracene, 1,6-double (allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-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-dimethylimine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Yttrium imine) propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-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-ene-2,3-dimethylimine), N,N'-p-( 2-hydroxy) xylylene-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-dimethylpyrene Amine), 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]hept-5-ene-2,3-dimethylimine), N,N'- P-(2,3-dihydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-bis[4 -{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-2-hydroxy-phenoxy}phenyl]propane, bis{4-(ene Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dimethylimine)}phenoxymethylpropane, N,N',N"-tris(ethylidenemethylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Iridium imide) isocyanurate, and oligomers thereof and the like.

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

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-di Amidoxime)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine 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-dimethylimineimine)phenyl}methane, double {4-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}methane, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)phenyl}ether, double {4- (Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}anthracene.

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-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-di Amidoxime)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine 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-dimethylimineimine)phenyl}methane, double {4-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}methane, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)phenyl}methane.

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

Further, for example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond, from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one kind of compound or two or more types of compounds. Further, the alkenyl-substituted nadic quinone imine compound is not included in the compound having a radical polymerizable unsaturated double bond. From the viewpoint of the above, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 0.01 to 1.00, more preferably from 0.01 to 0.70, based on the weight ratio of the polyamic acid or a derivative thereof. More preferably, it is 0.01 to 0.50.

Further, from the viewpoint of reducing the ion density of the liquid crystal display element, suppressing the increase of the ion density with time, and suppressing the afterimage, the compound having a radical polymerizable unsaturated double bond is substituted with the alkenyl group in the nadic ylidene compound. The ratio is preferably from 0.1 to 10, and more preferably from 0.5 to 5, by weight.

Examples of the compound having a radical polymerizable unsaturated double bond include a (meth) acrylate, a (meth) acrylamide derivative such as (meth) acrylamide, and a bismaleimide ( ). The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (methyl). Dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Ester and 2-hydroxypropyl (meth)acrylate.

Specific examples of the difunctional (meth) acrylate include, for example, ethylene diacrylate, products of Atomic Synthetic Chemical Co., Ltd., ARONIX M-210, ARONIX M-240, and ARONIX M-6200, Nippon Chemical Co., Ltd. Products of the company 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 Kyoeisha Oil Chemical Industry Co., Ltd. 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, for example, 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, for example, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, N-n-propyl Methyl acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylamide , N-tetrahydrofurfuryl acryla mide, 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-propylene decyl acridine (N- Acryloyl piperidine), N-acryloyl pyrrolidine, N,N'-methylenebis acrylamide, N,N'-ethylenebis acrylamide, N,N'-di Hydroxyethylene 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- (two Aminoamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methylpropenamide, N-benzyl-2- Methyl acrylamide and N,N'-methylene bis methacrylamide.

Among the (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).

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by KI CHEMICAL INDUSTRY Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, and BMI-5000 manufactured by Daiwa Kasei Kogyo Co., Ltd. And BMI-7000.

Further, for example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The oxazine compound may be one compound or two or more compounds. From the above viewpoints, the content of the oxazine compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, even more preferably 1 to 40% by weight, more preferably 1% by weight to 20% by weight.

The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves polyglycine or a derivative thereof and which has ring-opening polymerizability.

Further, the number of the oxazine structure in the oxazine compound is not particularly limited.

Regarding the structure of the oxazine, various structures are known. In the present invention, the structure of the oxazine is not particularly limited, and the oxazine structure in the oxazine compound may include a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The oxazine structure of the aromatic group.

The oxazine compound may, for example, be a compound represented by the following formula (a) to formula (f). Further, in the following formula, the bond represented by the center of the ring means that it is bonded to any of the carbon constituting the ring and capable of bonding the substituent.

In the above formula (a) to formula (c), R ¹ and R ^{2 each} represent an organic group having 1 to 30 carbon atoms. Further, in the above formulae (a) to (f), R ³ to R ⁶ represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. Further, in the above formula (c), formula (d) and formula (f), X represents a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH -, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH ₂ ) _m -S-. Here, m is an integer of 1 to 6. Further, in the above formula (e) and formula (f), Y independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF _{3 2} - or an alkylene group having 1 to 3 carbon atoms. The hydrogen bonded to the benzene ring or the naphthalene ring of Y may be independently substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ .

Further, the oxazine compound includes an oligomer or a polymer having an oxazine structure in a side chain, an oligomer or a polymer having an oxazine structure in the main chain.

Examples of the oxazine compound represented by the formula (a) include the following oxazine compounds.

In the formula, R ¹ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (b) may, for example, be the following oxazine compound.

In the formula, R ¹ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the following formula (I) is exemplified by the oxazine compound represented by the formula (I).

In the above formula (I), R ¹ and R ² represent an organic group having 1 to 30 carbon atoms, R ³ to R ⁶ represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -SO ₂ - or -C(CF ₃ ) ₂ -. The oxazine compound represented by the above formula (I) is exemplified by the following oxazine compound.

In the formula, R ¹ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (d) include the following oxazine compounds.

The oxazine compound represented by the formula (e) includes, for example, the following oxazine compounds.

Examples of the oxazine compound represented by the formula (f) include the following oxazine compounds.

Among these oxazine compounds, more preferably, formula (b-1), formula (c-1), formula (c-3), formula (c-5), formula (c-7), or formula (c-9), the evil represented by the formula (d-1) to the formula (d-6), the formula (e-3), the formula (e-4), and the formula (f-2) to the formula (f-4) Azin compound.

The oxazine compound can be produced by the same method as that described in the pamphlet of International Publication No. 2004/009708, Japanese Patent Laid-Open No. Hei 11-12258, and Japanese Patent Laid-Open No. 2004-352670.

For example, the oxazine compound represented by the general formula (a) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (refer to International Publication No. 2004/009708 pamphlet).

Further, the oxazine compound represented by the formula (b) can be obtained by a method of slowly adding a primary amine to formaldehyde, and then adding a compound having a naphthol-based hydroxyl group to carry out a reaction. (Refer to International Publication No. 2004/009708 booklet).

Further, the oxazine compound represented by the general formula (c) can be obtained by the following method: in the presence of an aliphatic secondary amine, an aliphatic tertiary amine or a basic nitrogen-containing heterocyclic compound in an organic solvent, 1 The mol phenol compound is reacted with respect to one aldehyde having at least 2 mol or more of phenolic hydroxyl groups, and 1 mol of the amine (refer to International Publication No. 2004/009708 pamphlet and Japanese Patent Laid-Open No. 11-12258 Bulletin).

Further, the oxazine compound represented by the general formula (d) to the general formula (f) can be obtained by having a plurality of benzene rings and bonding benzene with 4,4'-diaminodiphenylmethane or the like. a diamine of a ring organic group, an aldehyde such as formalin, or a phenol in a n-butanol, and a dehydration condensation reaction at a temperature of 90 ° C or higher (refer to Japanese Patent Laid-Open No. 2004-352670) Bulletin).

Further, for example, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the oxazoline compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, even more preferably the polyaminic acid or a derivative thereof, and further preferably It is 1% by weight to 20% by weight. Alternatively, from the above viewpoint, the content of the oxazoline compound is preferably such that when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the poly-proline or a derivative thereof is used. It is from 0.1% by weight to 40% by weight.

The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more oxazoline structures in one compound. Further, the oxazoline compound may have one oxazoline structure in one compound, and preferably has two or more oxazoline structures. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure on the side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two types having an oxazoline structure in a side chain or A copolymer of two or more monomers and a monomer having no oxazoline structure.

The oxazoline structure is preferably present in the oxazoline compound such that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polylysine.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline) and 1,2,4-tris-(2-oxazolinyl-2)-benzene (1,2,4). -tris-(2-oxazolinyl-2)-benzene), 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one (4-furan-2-yl methylene-2- phenyl-4H-oxazole-5-one), 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl) Benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6- Bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylene Bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline) and 2,2'-methylenebis(4- Phenyl-2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as EPOCROS (trade name, manufactured by Nippon Catalyst Co., Ltd.) may be mentioned.

More preferably, the oxazoline compound is exemplified by 2,2'-bis(2-oxazoline) and 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

Further, for example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The epoxy compound may be one compound or two or more compounds. From the above viewpoints, the content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, based on the polyamic acid or a derivative thereof, and further preferably 1% by weight to 20% by weight.

The epoxy compound may be exemplified by various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having an epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, and 3,3,3-trifluoro propylene oxide. Styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxy decane, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, table Epichlorohydrin, epibromohydrin, N,N-diglycidylaniline and 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 3, 4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

Examples of the compound having three epoxy rings in the molecule include 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([ 2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "TECHMORE VG3101L", manufactured by Mitsui Chemicals Co., Ltd.).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl group- M-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diamino Diphenylmethane and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

In addition to the compound, examples of the compound having an epoxy ring in the molecule include an oligomer or a polymer having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate. , (butyl) (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-epoxypropane)methyl (meth)acrylate N-cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexylmalanium. Imine-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate a glycidyl methacrylate copolymer, a (3-ethyl-3-epoxypropenyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

Among these examples, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N are particularly preferred. ,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "TECHMORE VG3101L", 3,4-epoxycyclohexenylmethyl-3',4 '-Epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamine, glycidyl isocyanurate, and chain fat. A family of epoxy compounds and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol-A epoxy compound. Hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, Phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolac type epoxy compound, brominated cresol novolac type epoxy compound, bisphenol A phenolic Varnish type epoxy compound, epoxy compound containing naphthalene skeleton, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, and more A polysulfide type diglycidyl ether compound and a biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

The glycidylamine may, for example, be a polyglycidylamine compound.

Examples of the epoxy group-containing acrylic compound include a homopolymer and a copolymer of a monomer having an oxirane group.

The glycidylamine can be exemplified by a glycidylamine type epoxy compound.

The chain aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound.

The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cyclic olefin compound.

Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all manufactured by Japanese epoxy resin), EPOTOHTO YD-128 (manufactured by Tohto Kasei Co., Ltd.), and DER-331. , DER-332, DER-324 (all manufactured by Dow Chemical), EPICLON 840, EPICLON 850, EPICLON 1050 (all manufactured by Dainippon Ink), EPOMIC R-140, EPOMIC R-301 and EPOMIC R-304 (both Made for Mitsui Chemicals).

Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by Japan epoxy resin), EPOTOHTO YDF-l70, EPOTOHTO YDF-175S, and EPOTOHTO YDF-2001 (all manufactured by Dongdu Chemical Co., Ltd.). , DER-354 (manufactured by Dow Chemical Co., Ltd.), EPICLON 830 and EPICLON 835 (all manufactured by Dainippon Ink).

The bisphenol type epoxy compound may, for example, be an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include SUNTOHTO ST-3000 (manufactured by Tohto Kasei Co., Ltd.), RIKARESIN HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and DENACOL EX-252 (manufactured by Nagase Chemtex Co., Ltd.).

Examples of the hydrogenated bisphenol type epoxy compound include an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the brominated bisphenol-A type epoxy compound include 5050 and 5051 (all manufactured by Japanese epoxy resin), EPOTOHTO YDB-360, and EPOTOHTO YDB-400 (all manufactured by Dongdu Chemical Co., Ltd.), DER-530. DER-538 (all manufactured by Dow Chemical Co., Ltd.), EPICLON 152 and EPICLON 153 (all manufactured by Dainippon Ink).

Examples of the phenol novolak-type epoxy compound include 152 and 154 (all manufactured by Japan Epoxy Resin), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431 and DEN438 (all manufactured by Dow Chemical Co., Ltd.), and EPICLONN- 770 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EPPN-201 and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Nippon Epoxy Resin), YDCN-701, YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), EPICLONN-665, and EPICLON N-695 (both Manufactured by Dainippon Ink Chemical Industry Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by Nippon Epoxy Resin Co., Ltd.) and EPICLONN-880 (manufactured by Dainippon Ink Chemicals Co., Ltd.).

Examples of the epoxy compound containing a naphthalene skeleton include EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and NC-7000 (Nippon Chemical Co., Ltd.). Manufacturing).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidy1 ether (the following structural formula E101) and catechol diglycidylether (structure E102 below). ), resorcinol diglycidyl ether (the following structural formula E103), tris(4-glycidoxyphenyl)methane (the following structural formula E105), 1031S, 1032H60 (all are Japanese rings) Oxygen resin manufacturing), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), DENACOL EX-201 (manufactured by Nagase Chemex), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.) TECHMORE VG3101L (manufactured by Mitsui Chemicals, Inc.), a compound represented by the following structural formula E106, and a compound represented by the following structural formula E107.

Examples of the biscyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by Dow Chemical Co., Ltd.) and EPICLON HP-7200 (manufactured by Dainippon Ink and Chemicals Co., Ltd.).

Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and RIKARESIN DME-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol diglycidyl ether (the following structural formula E109), and polyethylene glycol condensed water. Glycerol ether, propylene glycol diglycidyl ether (the following structural formula E110), tripropylene glycol diglycidyl ether (the following structural formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structural formula) E112), 1,4-butanediol diglycidyl ether (structure E113 below), 1,6-hexanediol diglycidyl ether (structure E114 below), dibromo neopentyl glycol diglycidyl Ether (Structure E115 below), DENACOL EX-810, DENACOL EX-851, DENACOL EX-8301, DENACOL EX-911, DENACOL EX-920, DENACOL EX-931, DENACOL EX-211, DENACOL EX-212, DENACOL EX-313 (all manufactured by Nagase Chemex), DD-503 (made by Asahi Kasei), RIKARESIN W-100 (Nippon Chemical and Chemical Manufacturing), 1,3,5,6-tetraglycidyl-2,4-hexyl Glycol (Structure E116 below), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polycondensate Oleyl ether, pentaerythritol polyglycidyl ether, DENACOL EX-313, DENACOL EX-611, DENACOL EX-321 and DENACOL EX-411 (both manufactured by Nagase Chemtex Corporation).

Examples of the polysulfide type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol).

Examples of the biphenol-based epoxy compound include YX-4000, YL-6121H (all manufactured by Japan Epoxy Resin), NC-3000P and NC-3000S (both manufactured by Nippon Kayaku Co., Ltd.).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117), diglycidyl phthalate (the following structural formula E118), and phthalic acid bis (2). -Methyl oxiranylmethyl)ester (the following structural formula E119), a compound represented by the following structural formula E121, a compound represented by the following structural formula E122, and a compound represented by the following structural formula E123.

Examples of the glycidyl ester epoxy compound include 871 and 872 (all manufactured by Japan Epoxy Resin), EPICLON 200, and EPICLON 400 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), DENACOL EX-711 and DENACOL. EX-721 (both manufactured by Nagase Chemex).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline (structure E124 below), N,N-diglycidyl-o-toluidine (structure E125 below), N, N-diglycidyl-m-toluidine (structure E126 below), N,N-diglycidyl-2,4,6-tribromoaniline (structure E127 below), 3-(N,N - diglycidyl) aminopropyltrimethoxydecane (structure E128 below), N,N,O-triglycidyl-p-aminophenol (structure E129 below), N,N,O-three Glycidyl-m-aminophenol (structure E130 below), N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (Mitsubishi Gas Chemical), the following structure Formula E132), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (Mitsubishi Gas Chemical), the following structural formula E133), 1,4-double (N, N-diglycidylaminomethyl)cyclohexane (the following structural formula E134), 1,3-bis(N,N-diglycidylamino)cyclohexane (the following structural formula E135), 1, 4-bis(N,N-diglycidylamino)cyclohexane (the following structural formula E136), 1,3-bis(N,N-diglycidylamino)benzene (the following structural formula E137), 1,4- Bis(N,N-diglycidylamino)benzene (structure E138 below), 2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane (described below) Structural formula E139), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (Strong formula E140 below), 2,2'-dimethyl-(N ,N,N',N'-tetraglycidyl)-4,4'-diaminodiphenyl (structure E141 below), N,N,N',N'-tetraglycidyl-4, 4'-Diaminodiphenyl ether (Formula E142 below), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (Structure of Formula E143 below) 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (formula E144 below), tris(4-(N,N-diglycidyl)aminophenyl) Methane (structure E145 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (Structure E146 below), 3,4,3',4' - Tetrakis(N,N-diglycidylamino)diphenyl ether (the following structural formula E147), a compound represented by the following structural formula E148, and a compound represented by the following structural formula E149.

The homopolymer of the monomer having an oxiranyl group may, for example, be polyglycidyl methacrylate. The copolymer of the monomer having an oxiranyl group may, for example, be N-phenylmaleimide-glycidyl methacrylate copolymer or N-cyclohexylmaleimide-methyl group. Glycidyl acrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-methacrylic acid shrinkage A glyceride copolymer, a (3-ethyl-3-epoxypropenyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

Examples of the monomer having an oxiranyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

In the copolymer of the monomer having an oxiranyl group, other than the monomer having an oxiranyl group, for example, (meth)acrylic acid or methyl (meth)acrylate may be mentioned. , ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid ring Hexyl ester, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (methyl) ) (3-ethyl-3-epoxypropenyl)methyl acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

The glycidyl isocyanurate may, for example, be 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (1) ,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, the following structural formula E150), 1,3-diglycidyl-5-ene Propyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (structural formula E151 below) and glycidyl isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and EPOLEAD PB3600 (manufactured by DAICEL Chemical Industry Co., Ltd.).

The cyclic aliphatic epoxy compound may, for example, be 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate ( The following structural formula E153), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (structure E154 below), ε-caprolactone modified 3,4-epoxy Cyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2:8,9-diepoxylimene (1,2:8,9-diepoxy limonene, CELLOXIDE 3000 (DAICEL Chemical Industry Shares) Manufactured by the company, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (CELLOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), the following structural formula E155 ), a compound represented by the following structural formula E156, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY Co., Ltd.), EHPD-3150 (manufactured by DAICEL Chemical Industry Co., Ltd.), and a cyclic aliphatic type Epoxy resin.

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and a low molecular compound, and can be selected and used according to the respective purposes.

For example, the polymer compound may be a polymer compound which is soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal alignment agent of the present invention from the viewpoint of controlling the electrical characteristics or the alignment property of the formed liquid crystal alignment film. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, and oxime. Polyurethane and anthrone modified polyester.

Further, for the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be mentioned when it is necessary to improve the antistatic property, and 3) when it is desired to improve the substrate. In the case of adhesion or rubbing resistance, a decane coupling agent or a titanium coupling agent may be mentioned, and 4) a ruthenium imidization catalyst may be mentioned when ruthenium 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-aminobenzene Triethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl A Dimethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyl Trimethoxydecane, N-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine, and N,N'-bis[3-(trimethoxydecyl) Propyl] ethylenediamine.

Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethylaniline, and methyl group. Aromatic amines such as aniline and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline a cyclic amine such as a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole, or a hydroxy-substituted imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine and isoquinoline. One or two or more.

The amount of the decane coupling agent to be added is usually from 0% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight based on the total mass 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, per mole of the carbonyl group of the polyglycolic acid or the derivative thereof.

The amount of the other additives to be added varies depending on the use thereof, and is usually from 0% by weight to 100% by weight, preferably from 0.1% by weight to 50% by weight based on the total mass of the polyamic acid or the derivative thereof.

Further, for example, the liquid crystal alignment agent of the present invention may further contain an acrylic polymer, an acrylate, in a range not detracting from the effects of the present invention (preferably, the amount of the polyamic acid or a derivative thereof within 20% by weight) A polymer, and other polymer components such as polyamidoximine which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or a derivative thereof and a diamine.

Further, for example, from the viewpoint of adjusting the coatability of the liquid crystal alignment agent and the concentration of the polyamic acid or a derivative thereof, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent can be used as long as it has a solvent capable of dissolving a polymer component, and is not particularly limited. The solvent widely includes a solvent used in a production step or a use of a polymer component such as polyaminic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be a solvent or a mixed solvent of two or more solvents.

The solvent may, for example, be a good solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability.

Examples of the aprotic polar organic solvent which is a good solvent with respect to the polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, dimethyl imidazolidinone, and N- N-methyl Caprolactam, N-methyl propionamide, N,N-dimethylacetamide, dimethyl sulfoxide, N, Lactones such as N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone.

Examples of the other solvent for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and B. Ethylene glycol monoalkyl ether such as diol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl a propylene glycol monoalkyl ether such as ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether; dialkyl malonate such as dipropyl malonate; dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether; An ester compound such as an analog.

Among these compounds, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, Propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

In the present invention, the concentration of the polymer component containing the polyamic acid or a derivative thereof in the liquid crystal alignment agent is not particularly limited, but is preferably 0.1% by weight to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, it is necessary to perform an operation of diluting the contained polymer component with a solvent in advance in order to adjust the film thickness. In this case, from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent, the concentration of the polymer component is preferably 40% by weight or less.

Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually 10% by weight or less. For other coating methods, such as a dipping method or an ink-jet method, it is possible to further reduce the concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the film thickness of the obtained liquid crystal alignment film tends to be an optimum thickness. Therefore, in a normal spin coating method, a printing method, or the like, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5% by weight to 10% by weight. However, depending on the method of applying the liquid crystal alignment agent, it may be used at a lower concentration.

Further, when the liquid crystal alignment agent of the present invention is used for producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to a mechanism or method for forming the liquid crystal alignment agent film. For example, when a film of a liquid crystal alignment agent is formed by a printing machine, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa ‧ s or 5 mPa ‧ s or more from the viewpoint of obtaining a sufficient film thickness, and from the viewpoint of suppressing uneven printing From the viewpoint of the liquid crystal alignment agent of the present invention, the viscosity is preferably 100 mPa ‧ s or 100 100 mPa ‧ s or less, and more preferably 10 mPa ‧ to 80 mPa ‧ s. When the liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa ‧ to 200 mPa ‧ s, and more preferably 10 mPa ‧ to 100 mPa from the same viewpoint ‧s. The viscosity of the liquid crystal alignment agent can be reduced by dilution of the solvent or aging with stirring.

The liquid crystal alignment agent of the present invention may be in the form of a polyglycine or a derivative thereof, or a form of a so-called polymer blend in which two or more kinds of polyaminic acid or a derivative thereof are mixed. The liquid crystal alignment agent in the form of a polymer blend may, for example, be a liquid crystal alignment agent containing polylysine or derivatives A and B thereof, and the polyamine or the derivative A thereof contains the diamine One or both of the diamine of the side chain structure and the polyamine or the derivatives of the derivatives A and B contain a diamine represented by the above formula (N).

Polyproline or a derivative thereof A is a polyamine or a derivative thereof containing the diamine having a side chain structure. Polylysine or a derivative thereof B is a polyamine or a derivative thereof containing a diamine other than a diamine having a side chain structure. The diamine represented by the above formula (N) may be contained in at least one polyphthalic acid or a derivative thereof mixed in the polymer blend, and may be contained in polylysine or a derivative thereof. Both A and B may also be included in all polyamines or derivatives thereof mixed in the polymer blend.

The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method of producing a liquid crystal alignment film from a liquid crystal alignment agent, for example, a step of forming a coating film of the liquid crystal alignment agent of the present invention, and a coating film of the liquid crystal alignment film of the present invention. It is obtained by the step of heating and calcining. For the liquid crystal alignment film of the present invention, the film obtained in the calcination step may be subjected to a rubbing treatment as needed.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention onto a substrate of a liquid crystal display element, similarly to the production of a usual liquid crystal alignment film. The substrate may be a glass substrate in which an electrode such as an Indium Tin Oxide (ITO) electrode or a color filter may be provided.

A method of applying a liquid crystal alignment agent onto a substrate 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 are equally applicable in the present invention.

The calcination of the coating film can be carried out under the conditions necessary for the polyhydric acid or a derivative thereof to undergo dehydration and ring closure reaction. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like. These methods are equally applicable in the present invention. It is usually preferred to carry out at a temperature of from about 150 ° C to about 300 ° C for from 1 minute to 3 hours.

The rubbing treatment can be carried out in the same manner as the rubbing treatment which is usually used for the alignment treatment of the liquid crystal alignment film, as long as the liquid crystal alignment film of the present invention can obtain sufficient retardation. Particularly preferred conditions are a hair injection amount of 0.2 mm to 0.8 mm, a stage moving speed of 5 mm/sec to 250 mm/sec, and a drum rotation speed of 500 rpm to 2,000 rpm. In the alignment treatment method of the liquid crystal alignment film, in addition to the rubbing method, a photoalignment method, a transfer method, or the like is generally known. These other alignment treatment methods may be used in combination in the rubbing treatment within the range in which the effects of the present invention can be obtained.

The liquid crystal alignment film of the present invention can be suitably obtained by a method including further steps other than the above steps. Such a further step may be a step of drying the coating film or a step of washing the film before and after the rubbing treatment with a washing liquid.

As in the calcining step, the drying step is generally known as a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, or the like. These methods are equally applicable in the drying step. The drying step is preferably carried out at a temperature within a range in which the solvent can evaporate, more preferably at a relatively low temperature compared to the temperature of the calcining step.

The cleaning method for cleaning the liquid crystal alignment film before and after the alignment treatment with a cleaning liquid may, for example, be brushing, jet spraying, steam cleaning or ultrasonic cleaning. These methods can be performed separately or in combination. The cleaning solution can be: pure water, or various alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, and xylene; halogen solvents such as methylene chloride; acetone and methyl ethyl Ketones such as ketones are not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently purified and has less impurities. Such a cleaning method can also be applied in the cleaning step of forming the liquid crystal alignment film of the present invention.

The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer.

A liquid crystal display device of the present invention has a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment for aligning the liquid crystal molecules in a predetermined direction membrane. The liquid crystal alignment film is a liquid crystal alignment film of the present invention.

The substrate may use the glass substrate described above for the liquid crystal alignment film of the present invention, and the electrode may use the ITO electrode formed on the glass substrate described above for the liquid crystal alignment film of the present invention.

The liquid crystal layer is formed by a liquid crystal composition sealed in a gap between a pair of opposing substrates, wherein the pair of opposite substrates form a liquid crystal alignment of one of the pair of substrates The face of the film faces oppositely toward the other substrate.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A liquid crystal composition which is positive in the dielectric anisotropy is exemplified in the following publications: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735 Japanese Patent Application Laid-Open No. Hei 8-- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), and Japanese Patent No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Wait.

The liquid crystal composition disclosed in the following publications is exemplified by the following Japanese Patent Publication No. Sho 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, and Japanese Patent Laid-Open No. 4 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Hei. No. Hei. Hei. Hei. Hei. Japanese Patent Laid-Open No. Hei 10-236990, Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Application Laid-Open No. Hei No. 10-236993, Japanese Patent Laid-Open No. Hei 10-236994 Japanese Patent Laid-Open No. Hei 10-237004, Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Laid-Open No. Hei 10 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 10-287. Japanese Patent Laid-Open No. Hei 10-291945, Japanese Patent Laid-Open No. Hei 11-029581, Japanese Patent Laid-Open No. Hei 11-080049, Japanese Patent Laid-Open Publication No. 2000-256307, Japanese Patent Laid-Open Publication No. 2001-019965, Japanese Patent JP-A-2001-072626, JP-A-2001-192657, and the like.

The liquid crystal composition in which the dielectric anisotropy is positive or negative does not have any influence even if one or more optically active compounds are added.

The liquid crystal display element of the present invention is obtained by forming a liquid crystal alignment film of the present invention on at least one of a pair of substrates such that the liquid crystal alignment film faces inward and the obtained pair of substrates are spaced apart The spacers are opposed to each other, and a liquid crystal composition is sealed in a gap formed between the substrates to form a liquid crystal layer. In the manufacturing process of the liquid crystal display element of the present invention, a step of attaching a polarizing film or the like to the substrate may be further included as needed.

The liquid crystal display element of the present invention can form liquid crystal display elements for various electric field methods. The liquid crystal display element for the electric field method includes a liquid crystal display element for applying a voltage to the liquid crystal layer in a direction in which the electrode is horizontal with respect to the surface of the substrate, or the electrode is A liquid crystal display element for a vertical electric field method in which a voltage is applied to the liquid crystal layer in a direction perpendicular to the surface of the substrate.

The liquid crystal display element for a lateral electric field method may not exhibit a large pretilt angle. Therefore, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a transverse electric field mode, wherein the liquid crystal of the present invention The alignment agent contains a poly-proline or a derivative thereof having no side chain structure such as polylysine obtained by a diamine having no diamine having a side chain structure or a derivative thereof.

The liquid crystal display element for the vertical electric field method needs to exhibit a large pretilt angle. Therefore, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a vertical electric field mode, wherein the liquid crystal alignment agent of the present invention contains A polyamic acid having a side chain structure or a derivative thereof, such as polylysine obtained by a diamine having a diamine having a side chain structure or a derivative thereof.

As described above, the liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be suitably applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer which is a raw material.

The liquid crystal display element of the present invention may further have elements other than the constituent elements. In such a liquid crystal display element of the present invention, a constituent element which is generally used in a liquid crystal display element such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit can be mounted.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. The compounds used in the examples are as follows.

<tetracarboxylic dianhydride>

Compound (1): Pyromellitic Dianhydride: PMDA

Compound (19): 1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBDA

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

Compound (37): 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1 ,3-dione (1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphoto[1,2-c]furan-1,3-dione) :TDA

Compound (49): 2,3,5-tricarboxycyclopentyl acetic dianhydride: TCMP

<Diamine>

Compound: 1,4-bis(4-aminophenyl)-1,4-diazacyclohexane (1,4-bis(4-aminophenyl)-1,4-diazacyclohexane): DAC

Compound: 4,4'-(pyridazine-1,4-diyl)bis(2-methylaniline): 3MPDA

Compound: 1,4-bis(3-aminopropyl)pyridazine: APP

Compound: 4,4'-diaminodiphenylmethane: DDM

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

Compound: 1,1-bis[4-(4-aminophenoxy)phenyl]-4-[(4-heptylcyclohexyl)ethyl]cyclohexane: 7H2HBA

Compound: 1,1-bis[4-(4-aminophenoxy)phenyl-4-(trans-4-n-pentylcyclohexyl)cyclohexane (1,1-bis[4-(4- Aminophenoxy)phenyl-4-(trans-4-n-pentyl cyclohexyl)cyclohexane):5HHBA

Compound: 1,1-bis[4-(4-aminophenyl)methylphenyl]-4-n-heptylcyclohexane: 7HBZ

Compound: 1,3-bis(3-aminopropyl)tetramethy1disiloxane: APDS

Compound: bis(4-amino-2-methylphenyl)methane: MDT

Compound: N,N'-bis(4-aminophenyl)-N,N-dimethylethylenediamine: NN2DAMe

Compound: 3,6-diaminocarbazole: DACZ

<additive>

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

Compound: N, N'-dihydroxyethylene bis acrylamide: HEA

Compound: bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl)methane (bis(3-phenyl-3,4-dihydro-2H-1,3) -benzoxazine-6-yl)methan e):PBM

Compound: 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate: EHE

Compound: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane: EHS

Compound: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene: BOB

<solvent>

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

<1. Synthesis of polyaminic acid>

[Synthesis Example 1]

To a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen gas inlet, 3.651 g of a compound DAC and 54.0 g of dehydrated NMP were placed, and stirred and dissolved under a dry nitrogen stream. Next, 1.237 g of the compound (1), 1.112 g of the compound (19), and 15.0 g of dehydrated GBL 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, 25.0 g of BC was added to the obtained solution to obtain a polyglycine solution having a concentration of 6% by weight. This polyamic acid was used as PA1. PA1 has a weight average molecular weight of 34,800.

The weight average molecular weight of polylysine is determined in such a manner that the obtained polylysine is diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100:weight ratio) to make polylysine The concentration was about 1% by weight, and then the mixed solution was used as a developing solvent and measured by a GPC method using a 2695 separation module and a 2414 differential refractometer (manufactured by Waters), and converted to 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 31]

A polyphthalic acid solution (PA2) to a polyaminic acid solution (PA31) was prepared according to Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Tables 1 and 2. Synthesis Example 1 was included, and the results are summarized in Tables 1 and 2. In Synthesis Example 24 to Synthesis Example 28, since precipitates were precipitated during the reaction, polyamine acid could not be synthesized.

<2. Production of liquid crystal display element>

[Example 1]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

<Method of Manufacturing Liquid Crystal Display Element>

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 to form a liquid crystal alignment film. Next, the surface of the substrate on which the liquid crystal alignment film was formed was subjected to a rubbing treatment using a rubbing device to carry out an alignment treatment. Then, the liquid crystal alignment film was subjected to ultrasonic cleaning for 5 minutes in ultrapure water, and then dried in an oven at 120 ° C for 30 minutes.

A gap material of 7 μm was spread on one of the glass substrates so that the surface on which the liquid crystal alignment film was formed was inside and the rubbing direction was anti-parallel, and then sealed with an epoxy hardener to make a gap of 7 μm. Antiparallel cell. A liquid crystal composition shown below was injected into the unit, and a light curing agent was used to seal the injection port. Next, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element.

[Embodiment 2]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 3]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 4]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 5]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 6]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA6) having a concentration of 6 wt% synthesized in Synthesis Example 6, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 7]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA7) having a concentration of 6% by weight synthesized in Synthesis Example 7, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 8]

A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, 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 (PA13) having a concentration of 6 wt% synthesized in Synthesis Example 13 and the polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 10]

A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polyglycine solution (PA15) having a concentration of 6 wt% synthesized in Synthesis Example 15 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 11]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA8) having a concentration of 6 wt% synthesized in Synthesis Example 8, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 12]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA9) having a concentration of 6 wt% synthesized in Synthesis Example 9, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 13]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA10) having a concentration of 6 wt% synthesized in Synthesis Example 10, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 14]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA12) having a concentration of 6 wt% synthesized in Synthesis Example 12, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 15]

A mixed solvent of NMP.BC = 1/1 (weight ratio) was added to a polyglycine solution (PA13) having a concentration of 6% by weight synthesized in Synthesis Example 13, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 16]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA14) having a concentration of 6 wt% synthesized in Synthesis Example 14, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 17]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA15) having a concentration of 6 wt% synthesized in Synthesis Example 15, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 18]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA16) having a concentration of 6 wt% synthesized in Synthesis Example 16, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Embodiment 19]

A mixed solvent of N MP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA17) having a concentration of 6% by weight synthesized in Synthesis Example 17, and the whole was diluted to 4% by weight. Liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 20]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA18) having a concentration of 6 wt% synthesized in Synthesis Example 18, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 21]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA19) having a concentration of 6 wt% synthesized in Synthesis Example 19, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 22]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA20) having a concentration of 6 wt% synthesized in Synthesis Example 20, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 23]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA21) having a concentration of 6 wt% synthesized in Synthesis Example 21, and the whole was diluted to 4 wt% to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 24]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA22) having a concentration of 6 wt% synthesized in Synthesis Example 22, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 25]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA23) having a concentration of 6 wt% synthesized in Synthesis Example 23, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 26]

To the polyglycine solution (PA22) having a concentration of 6% by weight synthesized in Synthesis Example 22, 20% by weight of BOB equivalent to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 27]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA11) having a concentration of 6 wt% synthesized in Synthesis Example 11, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 28]

To the polyglycine solution (PA19) having a concentration of 6% by weight synthesized in Synthesis Example 19, 20% by weight of BANI-M corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 29]

To the polyglycine solution (PA19) having a concentration of 6% by weight synthesized in Synthesis Example 19, 20% by weight of HEA equivalent to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 30]

To the polyglycine solution (PA21) having a concentration of 6% by weight synthesized in Synthesis Example 21, 20% by weight of PBM corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 31]

To the polyglycine solution (PA21) having a concentration of 6% by weight synthesized in Synthesis Example 21, 20% by weight of BANI-M corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 32]

To the polyglycine solution (PA21) having a concentration of 6 wt% synthesized in Synthesis Example 21, 20 wt% of PBM corresponding to the weight of the polymer and EHS equivalent to 10 wt% of the weight of the polymer were added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 33]

To the polyglycine solution (PA9) having a concentration of 6% by weight synthesized in Synthesis Example 9, 20% by weight of BANI-M, based on the weight of the polymer, and 10% by weight of EHS, based on the weight of the polymer, were added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 34]

To the polyglycine solution (PA11) having a concentration of 6% by weight synthesized in Synthesis Example 11, 10% by weight of EHE equivalent to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 1]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA29) having a concentration of 6 wt% synthesized in Synthesis Example 29, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, 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]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA30) having a concentration of 6 wt% synthesized in Synthesis Example 30, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 3]

A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA31) having a concentration of 6 wt% synthesized in Synthesis Example 31, and the whole was diluted to 4% by weight to prepare a liquid crystal. An aligning agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 4]

The polyglycine solution (PA29) having a concentration of 6 wt% synthesized in Synthesis Example 29 and the polyglycine solution (PA30) having a concentration of 6 wt% synthesized in Synthesis Example 30 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 5]

A polyglycine solution (PA29) having a concentration of 6% by weight synthesized in Synthesis Example 29 and a polyglycine solution (PA31) having a concentration of 6% by weight synthesized in Synthesis Example 31 were weighed at 8/2. More than mixing. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

<3. Evaluation of electrical characteristics>

The liquid crystal display elements produced in Examples 1 to 34 and Comparative Examples 1 to 5 were subjected to measurement of ion density and measurement of long-term reliability in the following manner.

1) Determination of ion density

The ion density was measured using a liquid crystal property evaluation device 6254 manufactured by TOYO Technica. The measurement conditions were set such that 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 3.

2) Determination of retention characteristics of ion density

The ion density [pC] of the liquid crystal display element produced was determined over time, and the retention characteristics were evaluated. The test method for maintaining the characteristics was to measure the ion density [pC] by placing the liquid crystal display element in an environment at a temperature of 100 ° C and taking it out over time. The smaller the increase in ion density (for example, the amount of increase is less than 100: the amount of increase = the ion density after 500 hours - the ion density of the initial (0 hour)), it can be said that the retention characteristic of the ion density is better, and it can be said that the electrical characteristics are The better the long-term reliability. The data after 300 hours and after 500 hours are shown in Table 3.

As shown in Table 3, the liquid crystal display element using a liquid crystal alignment film obtained by a liquid crystal alignment agent containing a polyamic acid containing a DAC in a monomer has a markedly improved effect of suppressing an increase in ion density with time.

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 (27)

A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent being characterized in that the diamine is selected from the following structural formula (N) -1~ one or more of the groups consisting of the compounds represented by the structural formula (N)-28: The liquid crystal alignment agent according to claim 1, wherein the diamine is selected from the group consisting of the following structural formula (N)-1, structural formula (N)-2, and structural formula (N)-5. ~Structure formula (N)-7, structural formula (N)-9, structural formula (N)-10, structural formula (N)-14, structural formula (N)-17, structural formula (N)-18, structure One or more of the groups consisting of the compounds represented by the formula (N)-21 to the structural formula (N)-23, the structural formula (N)-26, and the structural formula (N)-28: The liquid crystal alignment agent according to claim 2, wherein the diamine represented by the general formula (N) is a compound represented by the structural formula (N)-1 and the structural formula (N)-2. One or both of them. The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises a side chain structure represented by the following general formula (VIII) and general formula (X) to general formula (XIII). Diamine: (In the formula (VIII), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m - (m represents an integer of 1 to 6) R ¹ represents a group having a steroid skeleton, and a group represented by the following formula (IX). When the positional relationship of two amino groups bonded to the benzene ring is para, R ¹ further contains a carbon number of 1 The alkyl group of ~30, when the positional relationship is meta, R ¹ further comprises an alkyl group having 1 to 30 carbon atoms or a phenyl group, and any -CH ₂ - in the alkyl group may independently pass through - CF ₂ -, -CHF-, -O- (here non-continuous), -CH=CH- or -C≡C-, -CH ₃ may be via -CH ₂ F, -CHF ₂ or -CF ₃ Substituted, the hydrogen of the phenyl group may be independently substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ ); (In the formula (IX), A ⁴ and A ⁵ each independently represent a single bond, -O- (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon The number is from 1 to 12, and R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3 - Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or hydrazine- 9,10-diyl, R ⁴ represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b respectively represent integers of 0 to 4, c, d, and e represent integers of 0 to 3, respectively, and f and g independently represent 0 to 2, respectively. Integer, and c+d+e≧1); (In the general formulae (X) and (XI), R ⁵ independently represents -H or -CH ₃ , R ⁶ represents -H, or an alkyl group or an alkenyl group having 1 to 20 carbon atoms, and A ⁶ independently represents a single a bond, -C(=O)- or -CH ₂ -, in the formula (XI), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group; (In the general formulae (XII) and (XIII), A ⁷ independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and in the formula (XII), R ⁹ represents -H or the carbon number is 1~. An alkyl group of 30, wherein any -CH ₂ - of the alkyl group having 2 to 30 carbon atoms may be -O- (here, discontinuous), -CH=CH- or -C≡C- Substituted, A ⁸ represents a single bond or an alkylene group having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexylene, and h represents 0 or 1, and formula (XIII) In the formula, R ¹⁰ represents an alkyl group having 6 to 22 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 22 carbon atoms. The liquid crystal alignment agent according to claim 4, wherein the diamine having a side chain structure is selected from the group consisting of the following formula (VIII-2) and formula (VIII-4). (VIII-6), at least one of the compounds represented by the formula (XII-2), the formula (XII-4), and the formula (XII-6): (In the above formula, R ²³ , R ²⁹ and R ³⁰ each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms). The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises a side chain structure represented by the following general formula (I) to formula (VII) and formula (XV). Diamine: H ₂ NX-NH ₂ (I) (In the formula (I), X represents -(CH ₂ ) _m - (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents Single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N (CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH _{2 m} -S-(m represents an integer of 1 to 6), and in the formula (V), Z represents a single bond or does not exist, and in the formula (XV), R ³³ and R ³⁴ each independently represent a carbon number of 1 ~3 alkyl or phenyl, A ³ independently represents a methylene group, a phenylene group or an alkyl substituted phenylene group; l represents an integer of 1 to 6, and m represents an integer of 1 to 10, II)~ In the formula (VII), the hydrogen bonded to the cyclohexane ring or the benzene ring may be independently substituted with -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H , -PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (IV) may be substituted by a benzyl group). The liquid crystal alignment agent according to claim 6, wherein the diamine having no side chain structure is selected from the following structural formula (IV-1), structural formula (IV-2), and structure. Formula (IV-15)~Structure Formula (IV-17), Structural Formula (V-1)~Structure Formula (V-12), Structural Formula (V-33), Structural Formula (V-35)~Structure Formula ( At least one of a compound represented by V-37), structural formula (VII-2), and structural formula (XV-1): The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 8, wherein the aromatic tetracarboxylic dianhydride is a structural formula (1), a structural formula (2), and a structural formula (5) to a structural formula. (7) and at least one of the compounds represented by the structural formula (14): The liquid crystal alignment agent according to claim 9, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the structural formula (1). The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride comprises one or both of an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 11, wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are represented by the following structural formula (19) and structural formula (23). At least one of the compounds represented by the structural formula (25), the structural formula (35) to the structural formula (39), the structural formula (44), and the structural formula (49): The liquid crystal alignment agent according to claim 12, wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the structural formula (19) and the structural formula (23). At least one of the compounds represented by the structural formula (37) and the structural formula (49). As described in any one of claims 4 to 13 a liquid crystal alignment agent, characterized in that the liquid crystal alignment agent contains the polyamic acid or derivatives A and B thereof, and the polyamic acid or derivative A thereof comprises the side having the diamine One or both of the polyamine of the chain structure and the polyamine of the polyamine or the derivatives A and B thereof contain a diamine represented by the formula (N). The liquid crystal alignment agent according to claim 1, wherein the liquid crystal alignment agent further contains a compound selected from an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and an oxazine. One or more of a compound, an oxazoline compound, and an epoxy compound. The liquid crystal alignment agent according to claim 15, wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine)phenyl}methane, N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl One of a group consisting of quinone imine) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) or More than one. The liquid crystal alignment agent according to claim 16, wherein the alkenyl-substituted nadicilide compound is bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine)phenyl}methane. The liquid crystal alignment agent according to claim 15, wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-methylenebis propylene amide, N, N '-Dihydroxyethylidene bispropene One or more of a group consisting of guanamine, ethylene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline). The liquid crystal alignment agent according to claim 18, wherein the compound having a radical polymerizable unsaturated double bond is N,N'-dihydroxyethylenebisacrylamide. The liquid crystal alignment agent according to claim 15, wherein the oxazine compound is selected from the group consisting of the following formula (b-1), formula (c-1), formula (c-3), and (c-5), formula (c-7), formula (c-9), formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula ( F-2) One or more of the groups consisting of the compounds represented by the formula (f-4): The liquid crystal alignment agent according to claim 20, wherein the oxazine compound is a compound represented by the formula (c-1). The liquid crystal alignment agent according to claim 15, wherein the oxazoline compound is 2,2'-bis(2-oxazoline) and 1,3- One or both of bis(4,5-dihydro-2-oxazolyl)benzene. The liquid crystal alignment agent according to claim 22, wherein the oxazoline compound is 1,3-bis(4,5-dihydro-2-oxazolyl)benzene. The liquid crystal alignment agent according to claim 15, wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1, 3 - bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2-[4 -(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]benzene Propane, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer And one or more of the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane. The liquid crystal alignment agent according to claim 24, wherein the epoxy compound is 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylic acid. Ester or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent according to any one of claims 1 to 25. A liquid crystal display element having a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction The liquid crystal display element is characterized by: The liquid crystal alignment film is a liquid crystal alignment film according to claim 26 of the patent application.