TW200813158A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

This invention provides a liquid crystal aligning agent for a liquid crystal display device, a liquid crystal alignment film formed by using the liquid crystal aligning agent and a liquid crystal display device having the liquid crystal alignment film. The liquid crystal alignment film for the liquid crystal display device could improve the long-term reliability of the electrical property in relation to the ion density and the variation of the ion density as time goes by. One or more polymers chosen from polyamic acid and its derivatives, alkenyl substituted nadimide compound and specific heterocyclic compound are mixed in the liquid crystal aligning agent. The liquid crystal aligning agent is molded to form a film-shape and baked to fabricate the liquid crystal alignment film, and thereby the liquid crystal display device having the liquid crystal alignment film is fabricated.

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film, wherein the liquid crystal alignment The agent is at least one polymer selected from the group consisting of polylysine and a derivative of the polyaminic acid, and an alkenyl group substituted with nadimide (ie, inner _5_norbornene _ At least an anthracene of a compound having a specific heterocyclic structure and a heterocyclic compound having a specific heterocyclic structure are formed by dissolving a modifier in a solvent in a solvent. [Prior Art] The liquid crystal display device is currently used in various liquid crystal display devices such as a notebook computer and a desktop computer, a display device, a viewfinder of a camera, and a projection display state. TV. Furthermore, it is also used in optoelectronics related components such as optical printer heads, optical Fourier transform elements, and light vdve. The I 1 liquid crystal display element generally has: (1) one pair of substrates disposed opposite to each other, (2) electrodes formed on one or both surfaces of opposite surfaces of the pair of substrates, and/or a pair of substrates a liquid crystal alignment film formed on each of the opposing faces, and (4) a liquid crystal layer formed between the pair of substrates. As a conventional liquid crystal display element, the mainstream is a display element using a nematic liquid crystal, and (1) a TN (Twisted Nematic) type liquid crystal head element which is twisted at 90 degrees, (2) usually perform a twist of 18 degrees or more (Super 6 200813158 24843pif

A Twisted Nematic 'super-twisted type liquid crystal display element', and (3) a so-called FT (Thin Film Transistor) type liquid crystal display element using a /π film %曰. These liquid crystal display elements can appropriately see that the angle of view of the image is narrow, and have the following drawbacks: when the oblique direction is viewed, the shellness and contrast are lowered and the brightness inversion in the halftone is generated.

In recent years, '(1) TN-TFT type liquid crystal display using optical compensation film, (2) VA f (^^ brain 1 Ali§nment, vertical alignment) type liquid crystal using vertical alignment and optical compensation film Display element, (3) MVA (Mulii D〇 main Vertical Alignment) type liquid crystal display element using vertical alignment and protrusion structure technology, or (4) IPS of transverse electric field effect mode (In_piane 8 by her_, Coplanar switching type liquid crystal display element, (5) ECB (Electrically Controlled Birefringence) type liquid crystal display element, (6) optically compensated bending (0ptically C〇mpensated Bend or Optically self-Compensated Birefringence) Techniques such as refracting; OCB) type liquid crystal display elements improve the problem of the viewing angle, and the improved technique is put to practical use or research. The technical development of the liquid crystal display element is not only achieved by the improvement of these driving modes and element structures, but also by the improvement of the components used for the liquid crystal display element. Among the constituent members used for the liquid crystal display element, in particular, the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element, and the role of the liquid crystal display element in improving the quality of the liquid crystal alignment film becomes more and more important. . The liquid crystal alignment film is prepared from a liquid crystal alignment agent. At present, the main use of 7 200813158 24843pif ^liquid crystal alignment agent 'refers to a solution of poly-proline or soluble polyimine in an organic solvent. By applying such a solution to a film on a substrate and heating it, a method of forming a film to form a polyimine-based alignment method has also been studied for various liquid crystal alignment agents other than poly-aramidic acid. It has not been put into practical use in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid-phase growth, electrical properties, optical properties, display properties, and the like.

The characteristics of the liquid crystal alignment film to improve the display quality of the liquid crystal display element are as follows. When the filament density is low, the voltage applied to the liquid crystal is lowered in the normal temperature, and as a result, the brightness is lowered, and the initial S' is not caused to f-sound. In addition, there is a problem that, for example, even if the soil is more controllable, the ion density (length) after the high-temperature accelerated test is also lowered. In the attempt to solve the above problems, the industry has recently proposed a number of methods. More than one of the poly-acid compositions containing AI ^^ used to form a liquid crystal alignment film with different physical properties (for example, fish, jn: a polymer comprising polyacrylic acid and polyamine) The varnish composition of the agent (for example, refer to Patent Document 3). Acid amine, three or more polylysines having different physical properties of t3, and a poly-clear compound (for example, refer to Document 4). A varnish composition of a southern molecular material, the polyamino acid (the diamine compound synthesized by the diterpene diamine compound) is known to be used in polyimine and polyamic acid varnishes. A technique of adding a low molecular weight epoxy resin (for example, refer to Patent Document 6). Further, there have been several techniques for solving the following problems: This problem includes improving the performance of a liquid crystal display device by adding an additive to polyamic acid. As such a technique, for example, a liquid crystal alignment agent containing a polyamic acid and a hardening accelerator having an oxazine structure or an ox xazine structure (for example, see Patent Document 7) Polylysine and alkenyl A liquid crystal alignment agent (for example, refer to Patent Documents 8 and 9) and a liquid crystal alignment agent containing a polyphthalic acid and an epoxy group-containing compound (for example, refer to Patent Documents 1 and η). In addition, the company has also proposed a number of techniques for improving the performance of liquid crystal display elements by adding an additive to a compound for photo-alignment. As such a technique, for example, it is possible to include dichroism. A composition for photo-alignment of a molecule and a compound having a bis-imino group as a radical polymerizable group (for example, see Patent Document 12).

However, with these prior art techniques, the problem of separation and reliability cannot be fully solved. For example, in Patent Document 7, evaporation, sublimation, and decomposition are carried out in the acid imidization at the time of g: :, and the effect of the rolling is not affected.

In the case of Patent Document 11, the problem also includes that the power plant in which the liquid crystal display element is produced in the ionic impurity is not related to the diachronic ion density in the case of the ionic impurity: 200813158 24843pif The reason is that ionic impurities are contained in the components, and, for example, when the liquid crystal display element is used as the liquid crystal display element, the liquid crystal is decomposed and shattered, and the ionic property is considered to be caused by the operation of the element. The specialization, the sacred change of the calendar. So - low production of liquid crystal display components when the components ^ ^: 1 technology, can effectively reduce the ionic impurity f of the duration of the 3 = impurities, however, X. Further research is still needed

乂 乂 乂 专利 专利 , , , , , , , 日本 日本 日本 193 193 193 193 193 193 193 193 193 193 193 193 193 193 193 193 193 193 61 61 61 61 61 61 61 61 61 61 61 61 61 61 61 61 61 61 61 〇 733 manual 5 patent document 5] Japanese Patent Laid-Open No. Hei-16263 No. [Patent Document 6] Japanese Patent Laid-Open Publication No. _189-No. [Patent Document 7] Japanese Patent Laid-Open No. Hei 9_3〇2225 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 9-269491. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2, No. 2-27-638. A liquid crystal alignment agent for a liquid crystal display element, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film, which have been improved over a long period of time. . [Description of the Invention] 10 200813158 24843pif (4) The present inventors have made an effort to solve the above problems. As a result, in the liquid crystal display element having the liquid crystal alignment film as follows, it is possible to give a person, == sub-compliance reliability: the liquid crystal distribution (4) is in the use of the package 3, |proline and the derivative of the poly-proline At least one polymer further comprises an alkenyl-substituted nadic acid ylide imine compound 盥 (tetra) oxythiazepine, xirane), oxocyclobutanol (qoxetan), 1 arane = irane), aziridine, σ Aphrodite, and chewable structure

The liquid crystal alignment of at least one of the modifiers in which a combination of the modifiers is combined to complete the present invention. Further, it has been found that a liquid crystal alignment film produced by appropriately selecting the polyamic acid and using the above liquid cation-aligning agent can be suitably applied to liquid crystal display elements of various display driving methods. The present invention includes the following constitution. [1] A liquid crystal alignment agent which is a liquid crystal alignment agent comprising polylysine or a derivative thereof, an alkenyl-substituted nadic acid ruthenium imine compound, and a heterocyclic compound, characterized in that the heterocyclic compound has One or more selected from the group consisting of oxirane, oxetane, thiirane, aziridine, oxazoline, and oxazine Heterocyclic structure. [2] The liquid crystal alignment agent according to [1], wherein the dilute group-substituted nadic acid ylide compound is a compound represented by the following formula (Ina). [Chemical 1] 200813158 24843pif

, (Ina) towel, RlR2 respectively represents chlorine, carbon number 12 = alkenyl group having 3 to 6 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, aryl group or fluorenyl group, and η represents 丨~2 An integer; and when n==1, r3 represents a carbon number of 1 to 12, a carbon number of 5 to δ, a carbon number of "an aryl group, a benzyl group, and a -(CqH2q> 〇r(QH2rG)" u_CsH2s+] (q, ^, s represent an integer of 2 to 6, respectively, t represents 〇 or i, u represents an integer of Busun). The polyoxyalkylene alkyl group represented by _(R)v_C6H4_R4 (v represents 〇 Or R represents a group of a C 1 to 4 alkyl group, R 4 represents a hydrogen or a C 1 to 4 alkyl group, and _C6H4-T-C6H5 (T represents _ch2...-c(CH3) 2. A group represented by -CO-, -S- or -SCV), or a group in which 1 to 3 hydrogens directly bonded to an aromatic ring are substituted with a hydroxyl group; when n = 2, R3 represents a carbon number 2 to 20 alkylene, cycloalkylene having 5 to 8 carbon atoms, a_(CqH2qO)t_(CrH2r〇VCsH2s_ (q, r, s represent an integer of 2 to 6, respectively, and t represents 0 or 1) , u represents a polyoxyalkylene group represented by an integer of 1 to 3 Å, an arylene having a carbon number of 6 to 12, and -(8)V-C6H4-R5- (V represents 0 or 1, and R and R5 respectively represent an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and -C6H4-T-C6H4· (T represents - The base represented by CH2-, -C(CH3)2-, -CO-, -〇-, -OC6H4_C(CH3)2_C6H4〇_, _S-, or -S〇2_), 12 200813158 24843pif or the The liquid crystal alignment agent according to the item [2], wherein the alkenyl-substituted nadic acid ruthenium imide compound comprises the following: One or more of the compounds represented by the structural formula (Working Na-1)~(Ina-3).

[4] The liquid crystal alignment agent according to [1] to [3], which is characterized in that it contains 1 to 1 part by weight based on 100 parts by weight of the polyaminic acid or its derivative (in total amount) Alkenyl substituted nadic acid ylide imine compound. [5] The liquid crystal alignment agent according to [1] to [4], wherein the heterocyclic compound comprises a compound having two or more four coat structures, and the liquid crystal alignment agent comprises or is relative to polyamic acid or 1 (8) parts by weight of the derivative thereof is a compound of 1 to 1 part by weight (based on the total amount). 13 200813158 24843pif [6] The liquid crystal alignment agent according to [1] to [5], poly-amic acid or a derivative thereof, and the tetra-red melting of the money as a component is: a diamine reaction for the amine component The polylysine obtained. [7] The liquid crystal alignment agent according to [6], which is characterized in that it contains an A component and a B component, and the acid component a contains an aromatic § under-reagent, and the aromatic tetra- lysine is It is selected from one or two of the groups consisting of the following structural formula (ι)', = acid two (7) and (14), and (5). The combination of the above

[8] The liquid crystal alignment agent according to [7], wherein the aromatic tetra-retensive dianhydride is a compound of the structural formula (1). [9] The liquid crystal alignment agent according to [7] or [8], wherein the acid B component comprises any one of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride or Two. [10] The liquid crystal alignment agent according to [9], characterized in that the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are selected from the following structural formula: 14 200813158 24843pif

One or two or more compounds of the group consisting of (19), (23), (25), (35) to (37), (39), (44), and (49). [Chemical 4]

m

[π] The liquid crystal alignment agent according to the item [10], wherein the alicyclic tetra-retensive dianhydride is a compound of the formula (19). [12] The liquid crystal alignment agent according to [6] to [11], wherein the amine component contains the component A alone or two components of the component A and the component B, and the component A of the amine is selected from the group consisting of One or two or more compounds represented by the formulae of the group consisting of the general formulae (I) to (ΥΠ). [化5] 15 200813158 24843pif Off - A1 ~ NH2

In the formula (I), A1 represents -(CH2)m. Here, m represents an integer of 1 to 12. Further, in the general formulae (m), (V), and (W), A is independently expressed as an early bond, -S02-, -CO-, -CONH-, -NHCO-, C(CH3)2-, _c(CF3). 2. _(CH2)m, -〇-(CH2)nr〇-, or. Here, m independently represents an integer of i to 12. Further, in the formula (VI), A2 independently represents a single bond, s_, _c〇_, _C(CH3)2_, -C(CF3)r or an alkylene group having a carbon number of 1 to fluorene. Further, the hydrogen bonded to the cyclohexane ring or the benzene ring in the formula (Π) to (w) may be independently substituted into _F, -CH3, -OH, -COOH, _S03H, -Ρ03Η2. Benzyl or 'hydroxybenzyl. [13] The liquid crystal alignment agent according to [12], characterized in that the amine 16 200813158 24843pif A component is selected from the following structural formulae (IV-1), (IV-2), (IV-15) One or two or more compounds of the group consisting of (IV-16), (V-1)~(V-12), (V-33), and (VI[-2). [Chemical 6]

17 200813158 24843pif

[14] The liquid crystal alignment agent according to [12] or [13] wherein the component B of the amine is selected from the group consisting of the following general formulae (M) to (M); One or more compounds represented by the general formula of the group. [化7] 18 200813158 24843pif

In the formula (Μ), R1 represents a single bond, -0_, -CO-, -COO_, -OCO-, _CONH-, -CH20...CF20- or -(CH2)e-, and e represents an integer of 1 to 6; R2 represents a group having a steroid skeleton, a group represented by the following formula (xm), an alkyl group having 1 to 30 carbon atoms, or a phenyl group; and when the carbon number of the alkylene group and the alkyl group is 2 or more, any -CH2- can also be independently -0-, 19 200813158 24843pif - (JH: cat 0, read ^ replaced (where oxygen is discontinuous), phenyl hydrogen can also be alone;, methyl, methoxy, - Fluoromethoxy, difluoromethoxy or difluoromethyl lactyl substitution, but excluding the case of RLR2. # - ί t General (K) towel, R independently represents hydrogen or methyl; r4 ^ 不虱 or carbon number 1~3G hetero base; R5 independently U single bond, _co_ or . = general formula (X) towel, Rj independently represents hydrogen or methyl; r4 ^ not 虱 or carbon number 1~ Alkyl; R5 independently represents a single bond, -co_ i, 33 and R7 independently represent gas, and 〜30

It is: a general formula (Χί) towel, R8 represents hydrogen or a carbon number of 1 to 3 Å, and any -CHr of an alkyl group having 2 or more turns may be independently _〇_, _CH or HI. ^<-substitution (wherein oxygen is discontinuous); R9 independently represents an extension of -0·m; ring A represents a phenyl or 1,4-quinone or Γ represents 0 or 1; b represents 〇, 1 or 2;, the standing representative carbon has a carbon number of 3 to a group, or a carbon number of - a fluorinated group; Rl2 independently represents "an alkyl group having an anisotropic number of 1 to 6; d independently represents 〇 or}. 8]

R1B (XIII)

ί \ / \ 1 (R1T)r 20 200813158 24843pif In the general formula (XIH), r]3, r14 and R15 each independently represent a single bond, -Ο-, -COO-, -〇c〇·, -CONH- , an alkylene group having a charcoal number of 1 to 4, an oxygen alkyl group having a carbon number of 1 to 3 (in which oxygen is not accelerated), or a carbon number of 1 to 3 (wherein oxygen is discontinuous); ri6 And R independently represent hydrogen, fluorine or methyl; R18 represents hydrogen, fluorine, chlorine, cyano, an alkyl group having a carbon number of i to 30, an alkoxy group having a carbon number of from 1 to 30, and a carbon number of from 2 to 30. Alkoxyalkyl, monofluoromethyl, difluorodecyl, trifluorof-, monofluoromethoxy, difluoromethoxy or trifluoromethoxy; alkyl or alkoxy having 2 or more carbon atoms And any of the calcined bases may be substituted by a di-halogenethylene group or a group represented by the following formula (XIV); the ring and ring C each independently represent 1, 'phenylene Or ι, 4-cyclohexyl; f, g, and h each independently represent an integer of 0 to 4; i, j, and k each independently represent an integer of 〇 〜 3, and the total of these values is 1 or more; And m respectively represent 1 or 2 〇 [Chemical 9]

In the formula (XIV), R19, R20, R21 and R22 each independently represent a carbon group having 1 to 10 carbon atoms, or the group 'n' represents an integer of 1 to 1 Å. [15] The liquid crystal alignment agent according to [14], wherein the B component of the amine is selected from the group consisting of the following formula (Qingyi 2), (泗~4), (view 5) One or two of the groups consisting of (M-6), (XI-2), and (along a-4) 21 200813158 24843pif Compounds represented by the above formula. [化10]

In the formula, R23 independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R29 represents an alkyl group of hydrazine or a carbon number 丨~sun, and R30 represents hydrogen or a carbon number of 1 to 20. alkyl. [16] The liquid crystal alignment agent according to [1] to [15], which is characterized in that it contains two or more kinds of polyaminic acid or a derivative thereof. [17] a liquid crystal alignment agent, which is a liquid crystal alignment agent comprising polylysine or a derivative thereof, an alkenyl-substituted nadic acid ruthenium imine compound, and a heterocyclic compound, wherein the polyamine acid or The derivative is a polyimidonic acid obtained by reacting a tetradecanoic dianhydride as an acid component with a diamine as an amine component. 22 200813158 The acid component contains the component A and the component B, and the a component of the acid is selected from the following One or more compounds of the group consisting of structural formulae (1), (2), (5) to (7), and (14), the B component of the acid is selected from the following formulas (19), (23) One or two or more compounds of the group consisting of (25), (35) to (37), (39), (44), and (49), wherein the amine component separately contains the component A or contains the component A and B. The two components of the component, the A component of the amine, are selected from the following structural formulas -2), (rV-l5), (IV-16), (v-1)~(v_i2), (v33) and (VH- 2) One or two or more compounds of the group constituted by the group, the B component of the amine is selected from the group consisting of the following formula (view 2), (ship ~ 4), (Shan Yi 5), (view one 6), (χι_2) and (χι_4) a compound represented by one or two or more formulas, a subterranean substituted, or a benzoic acid imine compound containing one or two

- the heterocyclic compound has a group selected from the group consisting of ethylene oxide (five), oxetane, thUrane, apocytidine, and sputum itTi Or more than two heterocyclic structures.

23 200813158 24843pif [Chem. 12]

(19) (23) (25) (35)

24 200813158 24843pif [Chem. 13]

fV-10)

Nh2 h2n

NH (V, 12)

HO OH

(V-33)

(Vfi-2) 25 200813158 24843pif [Chem. 14]

In the formula, R23 independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R29 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R3G represents hydrogen or a carbon number of 1 to 20 carbon atoms. alkyl. [化15]

26 200813158 24843pif

[18] The liquid crystal alignment agent according to [17], wherein the acid component A is a compound represented by the structural formula (1), and the acid B component is represented by the structural formula (19). The compound A, the A component of the amine is one or two or more compounds represented by the structural formulas (iv-16), (V-1), (v-7) and (YU-2), and the b component of the amine is One or two or more compounds represented by the formulae (Μ-5), (XI-2) and (X[-4), the alkenyl-substituted nadic acid imide compound is represented by the structural formula (Ina-1) The compound, the heterocyclic compound comprises a compound selected from the group consisting of 4, cardinyl bis(N,N-diglycidylaniline), (3-glycidoxypropyl)trimethoxysulfonate, (3-glycidyloxy) Propyl)methyl decyloxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy sylvestre, bis[(3-ethyl epoxypropyl decyloxy)methyl Benzene, 2,4,6-tris(1'-aziridine)-153,5-triazine, where 1^1^tetrathiopyranyl _4'4--aminodiphenyl $元,本乙细-co-2-isopropyl 基 嗯 坐 sits on the Lin), and double (3_phenyl_3,4-two _211-1,3- benzene Bing oxazin _6- yl) methyl burning a group consisting of two or more of the compounds. [19] A liquid crystal alignment film which is formed by injecting a liquid crystal alignment state as described in the items [1] to [18] 27 200813158 24843pif. [20] A liquid crystal display element which is an electrode formed on one surface or both surfaces of opposite surfaces of a facing substrate: ::: a liquid crystal alignment film formed on each of opposite surfaces of the substrate, The liquid crystal display element of the substrate=^=the night crystal layer is characterized in that the liquid crystal alignment film is a liquid crystal alignment film as described in [19]. According to the present invention, it is possible to provide a liquid of various driving modes in which the long-term reliability of the ionic density change is excellent in the ion density, and the components are not provided. [Embodiment] The liquid crystal alignment county-composition composition of the present invention comprises: a dilute base, a ', a wide-acid and an imine compound having a selected from the group consisting of ethylene oxide to oxirane, and an oxygen sulfonate (継 継 、 、 、 、 、 、 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 az az az az az az az az az az az az az az az az az az az az az One or more polymers of the substance. 1: The alkenyl group of the rabbit is substituted with the Nadick acid-based imine compound. ... See the "Alkenyl" substituted nadic acid ylide compound. The 刖4 dilute group replaces the nadic acid ylide imide compound, and the polyamic acid or derivative thereof and the compound of the heterobibic acid used in the present invention are preferably used. As such a silk-substituted nadic acid, for example, a compound represented by the following formula (ina) can be given. 28 200813158 24843pif [Chem. 16]

In the formula (I na), R) and R2 each represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or a benzyl group. , η represents an integer of 1 to 2. Further, in the formula (I na), when η = 1, R3 represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a fluorenyl group ( q, r, s represent an integer of 2 to 6, respectively, t represents 0 or 1, u represents an integer of 1 to 30, and represents a polyoxyalkylene alkyl group, -(RVQEU-R4 (v represents 〇 or i, r represents the alkyl group of the inverse number 1 to 4, R4 represents a hydrogen or a base of 5 carbon atoms of 1 to 4, and _〇6Η4·Τ_(:6Η5 (T represents _ch2-, _c) (ch3) a group represented by 2_, _CO-, or -S〇2_), or a group in which 1 to 3 hydrogens directly bonded to the aromatic ring of these groups are substituted with a hydroxyl group. Further, in the formula (Ina) When n = 2, R3 represents an alkylene group having a carbon number of 2 to 20, a cycloalkyl group having a carbon number of 5 to 8, and -(CqH2q〇)r(CrH2r0)u-CsH2s-(q, r, s respectively An integer representing 2 to 6, an integer represented by 0 or 1, u is an integer represented by poly), a aryl group of aryl (6), and an aryl group (ary ene), u_(R\_C6H4_R5 29 200813158 24843pif 〇 or 1, R and R5 represent a group represented by a carbon number of 1 to 4 or a ring alkyl group having a carbon number of 5 to 8, respectively, to represent a group represented by _CH2_, _C(CH3)2·, _co_, 〇_, _〇c6h4_c(ch3)2_C6h4〇, -S-, or -S〇2_), or direct bonding of these groups to the aromatic ring The above-mentioned alkenyl-substituted nadic acid imide compound, for example, as described in Japanese Patent No. 2729565, may be used by substituting a dilute group for nadic anhydride (nadic). And a compound obtained by synthesizing a derivative of the acid anhydride with a diamine at a temperature of 80 to 220 C at a temperature of from 5 to 20 ° C, and a commercially available compound, as a specific example of a rare base-substituted nadic acid ylide compound. For example, the compounds shown below are mentioned. N-Mercaptopropylbicyclo[2.2.1]hept-5-ene diimine, N-methylallylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine imine, N-mercapto-mercaptopropylbicyclo[2·2·1]hept-5-ene-2,3-diimine, N - mercaptomethylallylmethylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine, N-(2-ethylhexyl)allylbicyclo[2· 2·1]hept-5-ene-2,3-diimineimine, N-(2-ethylhexyl)allylmethylbicycloindole·2·1] -5-ene-2,3-diimineimine, N-allyl-allylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine, N- Allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl broth 30 200813158 24843pif imine, N-mercaptopropyl methallyl bicyclo [^^g -^ene^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ [2·2·1:^_54#_2,3_:ψ 醯 imine, Ν-isopropene·ylmercaptopropylbicyclo[2·2·ηg _5_ene_2,3_dimethyl hydrazine Imine, fluorene-cyclohexyl allyl bicyclo [2·2·η-glycolene 2,3 bis quinone imine, Ν-cyclohexyl-allyl fluorenylbicyclo[m]g _5_ Alkene-2,3-diimineimine, N-cyclohexyl·methallylbicycloindole: ^heptene: ene-^dimethylimine, phenyl-allyl bicyclo [2.2.1 Hept-5-ene-2,3-diimineimine, N-phenyl-allylhydrazylbicyclo ρ·2·ι]hept-5-ene-2,3-dimethylimine, Ν_Benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-diimine, Ν-benzyl-allylhydrylbicyclo[2·2·1]g- 5-ene-2,3-dimethyl hydrazine, hydrazine-benzyl- Allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν-(2'-hydroxyethyl)allylbicyclo[2·2·1]hept-5 -ene-2,3-dimethylimine, 31 200813158 24843pif 1^(2'-hydroxyethyl)allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine, light ethyl ethyl) decyl fine propyl double soil [2.2.1] hept-5- fine-2,3-dimethyl quinone imine, Ν-(2',2'-dimercapto hydroxypropyl Allylbicyclo[2·2·1]hept-5-ene-2,3-diimineimine, N-(2f,2^dimethyl-3'-hydroxypropyl)allyl Methyl bicyclo[2·2·1]hept-5-ene-2,3-dimethylimine, N_(2f,3丨-disoyl), propyl double bad [2·2·1 Geng_5-fine-2,3-dimethylimine, N-(2',3f-dihydroxypropyl)allylhydrylbicyclo[2.2.1]hept-5-ene-2,3 - Diimine, N-(3f-hydroxypropenyl)allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4f-hydroxycyclohexyl) Allyl indenylbicyclo[2·2·1]hept-5-ene-2,3-diindoleimine, N-(4f-hydroxyphenyl)allylbicyclo[2.2.1]hept-5 -ene-2,3-diimineimine, N-(4'-hydroxyphenyl)allylmethylbicyclo[2.2.1]hept-5-ene -2,3-diimine, N-(4f-hydroxyphenyl)nonylallylbicyclo[2·2·1]hept-5-ene-2,3-diindoleimine, N -(4f-hydroxyphenyl)nonylallylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimineimine, 32 200813158 24843pif N_(3'-hydroxyphenyl)ene Propylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine, Ν-(3'-hydroxyphenyl)allylhydrylbicyclo[2.2.1]hept-5-ene -2,3-diimine, Ν-(p-hydroxybenzyl)allylbicyclo[2·2·1]hept-5-ene-2,3-diindoleimine, n_{2H2L hydroxyethyl Oxy)ethyl}allylbicyclo[2·2·1]hept-5-ene-2,3-didecanoate, hydroxyethoxy)ethyl}allylhydrylbicyclo[2.2· 1]hept-5-ene-2,3-diimideimine, hydroxyethoxy)ethyl}mercaptopropylbicyclo[2·2·ΐ]hept-5-ene-2,3-di Brewing imine, N_{2'-(2f-hydroxyethoxy)ethyl}methylallylmethylbicyclo[2·2·1]hept-5-ene-2,3-dipyrene Amine, Ν-π{iphydroxyethoxy)ethoxy}ethyl]allylbicyclo[2.2.1]hept-5-fine·2,3-didecanoic acid imide, Ν_[2'_( 2'_(2" old ethoxy) ethoxy} ethyl] propylene Methylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimineimine, called 2'_{2'-(2"-carbyloxy)ethoxy}B Methylallylbicyclo[2·2·1]hept-5-ene-2,3-diimineimine, Ν] 4'-(4'-old phenyl isopropylidene)phenyl }allylbicyclohept-5-ene-2,3-diimineimine, Ν-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}allyl fluorenylbicyclo[2 ·2·1]hept-5-ene-2,3-diindoleimine, 33 200813158 24843pif N-{4'-(4'-p-phenylphenylidene)phenyl}methylallyl Bicyclo[2.2.1]hept-5-rare-2,3-dimethylmerimimine, and oligomers of these compounds; N,NM-ethyl bis(allylbicyclo[2.2.1]hept-5- Alkene 4,3-dimethylenimine), " N,N'-extended ethyl bis(allylhydrazinobicyclo[2·2·1]hept-5-ene_2,3_dimethylhydrazine Imine), N, NW, ethyl bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), Ν, Ν'-triazinyl bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-didecanoic acid imide), hexamethylene bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-didecanoic acid imide), hydrazine, Ν'-hexa Mercapto bis(allylmethylbicyclo[2·2·1]-5-ene-2,3-dimethylimine), N,Nf-dodedecylbis(allylbicyclo[2] ·2·1]hept-5-ene-2,3-diindoleimine), hydrazine, Ν'-docamethylene bis(allylhydrazinobicyclo[2·2·1]hept-5 -ene-2,3_diimide), N,Nf-cyclohexyl bis(dipropylbicyclo[2·2·1]hept-5-lean-2,3-dimethylimine) , Ν,Ν'-cyclohexyl bis(allylmethylbicyclo[2·2·1]heptene-2,3-carboximine;), 1,2-double {3,-(ene Propylbicyclo[2·2·1]hept-5-ene-2,3·diindoleimide) 34 200813158 24843pif propoxy}Ethylene, 1,2-double {3'-(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}ethane, 1,2-bis{3f-(mercaptopropylbicyclo[2.2.1] Hg-5-ene-2,3-diimineimine)propoxy}ethid, bis[2f-{3f-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethyl imidate) propoxy}ethyl] squara, bis[2'-{3'_(allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl sulfoxide Amine)propoxy}ethyl]scale, M-double {3f-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) Butane, M_double {3'_(allylmethylbicyclo[2.2.1]heptene-2,3-diimineimine)propoxy}butyl, N,N'- P-phenylene bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,Nf-p-phenylene bis(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine), N,Nf-inter)phenylbis(allylbicyclo[2·2·1]hept-5-ene-2,3 - dimethyl quinone imine), hydrazine, Ν'- 伸 基 bis (allylmethyl bicyclo [2.2.1] hept-5-ene-2,3-diimine), hydrazine, hydrazine '-{(1-methyl)-2,4-phenylene} bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,Nf- P-Benzyl bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di 35 200813158 24843pif formamidine), N,Nf-p-phenylenediyl bis(allyl) Indenylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, Ν'-m-phenylenediyl bis(allylbicyclo[2.2.1]hept-5- Alkene-2,3-diimine), hydrazine, Ν'-m-xylylene bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dioxime Amine), 2,2_bis[4^{4'_(allylbicyclo[2.2.1]hept-5-ene-2,3_dioxin Phenoxy}phenyl]dioxane, 2.2-bis[4'_{4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) benzene Oxy}phenyl]propane, 2.2-bis[4f-{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-diimideimine)phenyl} methane, double {4-(allyl Base bisbicyclo[2.2.1]hept-5-ene-2,3-diimineimine) phenyl}decane, bis{4-(decylallylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine imine) phenyl}decane, bis{4-(decylallylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diindole Imine)phenyl}methane, bis{4-(allylbicyclo[2·2·1]hept-5-ene-2,3-diimideimine)phenyl} ether, double {4-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine) 36 200813158 24843pif Phenyl}ether, double {4-(methylallylbicyclo[2·2 ·1]hept-5-ene-2,3-diimineimine) phenyl)ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imino)phenyl] stone, double {4_(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimineimine) phenyl , double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), benzyl, 1,6-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-diimineimine; h3-hydroxyhexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene-2, 3-diimineimine)-3,6-di-transyloxime, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine )-5_ hydroxycyclohexane, 1,5-bis{3f_(allylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine imine) propoxy}-3- Hydroxypentane, bismuth-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-2-hydroxybenzene, bis(allylhydrazinobicyclo[2· 2·1]hept-5-ene-2,3-dioxime]-2,5-ditridecylbenzene, anthracene, >Γ-p-(2-hydroxy)benzenedimethyl-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,Nf-p-(2-hydroxy)benzylidene·bis(allylhydrazino ring [2.2 .1]Geng 37 200813158 24843pif -5-ene-2,3-diimineimine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1] Hg-5-ene-2,3-diimineimine), N,N'-m-(2-hydroxy)benzodiazepine-bis(fluorenyl) Propylbicyclo[2·2·1]hept-5-ene-2,3-diimineimine), N, lsT-p-(2,3-dihydroxy)benzenedimethyl-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5_ Alkene-2,3-dimethylimine, light base, phenyl]propane, double {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Formamidine)-2-hydroxyphenyl}methane, bis{3-(allylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine)-4-hydroxyl Styyl ether, double {3-(mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine)-5-light phenyl}, 1,1 , 1-tris-K-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimine]}phenoxymethylpropane, 1^^', 1^' _Tri(vinyl methallyl bicyclo [2.2.1] hept-5-ene-2,3-diimide) isocyanurate, and oligomers of these compounds and the like. Further, the alkenyl-substituted nadic acid ruthenium imide compound used in the present invention may be a compound represented by the following structural formula containing an asymmetric stretching group and a stretching phenyl group. 38 200813158 24843pif [Chem. 17]

In the above alkenyl-substituted nadic acid ylidene imide compound to be used in the present invention, an alkenyl-substituted nadic acid ruthenium imide compound such as these may be used singly or as a mixture of two or more of these compounds. As the above alkenyl-substituted nadic acid ylidene imide compound, preferred compounds include the following compounds. N, NM-ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,NW-ethyl-bis(allylhydrazinobicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimineimine), 39 200813158 24843pif N, NM-ethyl-bis(methylallylbicyclo[2·2·1]hept-5-ene-2,3 - bisinimide), hydrazine, Ν'-trimethylene bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dioxanimine), N,Nf- Hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diindoleimine), anthracene, Ν'-hexamethylene-bis(allylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine), dodecamethylene-bis(allylbicyclo[2·2·1]nonene-2,3- Dimethyl imine), hydrazine, Ν'-taudecyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-enedimethylanilide), hydrazine, Ν'-ring extension Hexyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylindoleimine), N,NL cyclohexyl-bis(allylhydrazinobicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine), fluorene, fluorene-p-phenyl-bis(allylbicyclo[2·2·1]hept-5-ene-2,3- Dimethyl imine:), N, Nf-p-phenylene-double ( Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,Nf_inter)phenyl-bis(allylbicyclo[2·2·1]g -5-ene-2,3-diimine), hydrazine, Ν'-inter)phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di曱醯imine), 40 200813158 24843pif N,N,-{(1-methyl)-2,4-phenylphenyl bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -dimethylimine), N,NL-p-phenylenediyl-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-diimide), N, Nf - p-Benzyl-bis(allyl-decylbicyclo[2.2.1]heptene-2,3-diimineimine), hydrazine, Ν'-m-phenylenedi-yl-bis(allyl Bicyclo[2·2·1]hept-5-ene-2,3-carboximine), hydrazine, Ν'-m-xylylene-bis(allylhydrazinobicyclo[2.2.1] Hg-5-ene-2,3-diimineimine), 2,2·bis[4'-{4'-(allylbicyclo[2·2·1]hept-5-ene_2, 3_diimine imine)phenoxy}phenyl]propane, 2,2_bis[4'-{4'-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3-diimineimine)phenoxy}phenyl]propane, 2,2-bis[4f-{4'-(mercaptopropylbicyclo[2·2·1]hept-5-ene Mercaptoimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine)phenyl} methane, double {4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimineimine) phenyl}decane, bis{4-(decylallylbicyclo[2.2 .1]hept-5-ene-2,3-carboximine) phenyl}decane, bis{4-(methallylhydrazinobicyclo[2.2.1]hept-5-ene-2 ,3-diindoleimine)phenyl}methane, 41 200813158 24843pif bis{4-(allylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine) benzene }, double {4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimideimine) phenyl}ether, double {4-(decyl allyl Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine) phenyl}ether, bis{4-(allylbicyclo[2·2·1]hept-5-ene- 2,3-diindoleimine)phenyl} stone wind, double {4-(allylhydrazinobicyclo[2-2-1]hept-5-ene-2,3-diimineimine) Phenyl}•sulfone, double {4-(mercaptopropylbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine) phenyl}. As the above alkenyl-substituted nadic acid ylidene imide compound, preferred compounds include the following compounds. Ν,Ν'-extended ethyl-bis(allylbicyclo[2·2·1]hept-5-enedimethylanilide), N,Nf-extended ethyl-bis(allylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dimethylimine), hydrazine, Ν'-extended ethyl-bis(methylallylbicyclo[2·2·1]hept-5_ Alkene-2,3-diimineimine), N,Nf_trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N , N'_hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), 42 200813158 24843pif N,N'-hexamethylene-based Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,N'-dodedecyl-bis(allylbicyclo[2· 2·1]hept-5-ene-2,3-diimineimine), hydrazine, ίνΓ-taudecyl-bis(allylhydrylbicyclo[2.2.1]hept-5-ene- 2,3-diimine), hydrazine, Ν'-cyclohexyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'-cyclohexyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, Ν'-p-phenylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, hydrazine - p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), fluorene, Ν'-interphenylene-bis(allyl Bicyclo[2·2·1]hept-5-ene-2,3-diimineimine), fluorene, Ν'-inter)phenyl-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dimethylimine), hydrazine, Ν4(1-indenyl)-2, phenylphenyl}bis(allylbicyclo[2·2·1]hept-5- Alkene-2,3-dimethylimine), hydrazine, Ν'-p-phenylenediyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimine ), N,Nf-p-xylylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), 43 200813158 24843pif N,N'- m-Benzadienyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,Nf-m-benzodiazepine-bis(allylhydrazine) Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine), 2.2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine imine)phenoxy}phenyl]propane, 2.2-bis[4'-{44allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3 _ dimethyl fc imine) phenoxy} phenyl] propyl, 2.2- bis [4 ^ {4, stomach (methylallyl bicyclo [ 2.2.1]hept-5-ene-2,3-dimethyl phthalimide)phenoxy}phenyl]propane, double {4-(allylbicyclo[2.2.1]hept-5-ene -2,3_diimine)phenyl}methane, bis{4-(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) phenyl }methane, bis{4-(decylallylbiscyclo[2.2.1]hept-5-ene-2,3-dimethylimine) phenyl}decane, double {4-(decyl allylic Base bisbicyclo[2·2·1]hept-5-ene-2,3-dimethylimine)phenyl}methane. The compound which is more preferable than the above-mentioned alkenyl-substituted nadic acid ylidene imide compound is exemplified by a double {4-(allylbicyclo[2·2·1]g which is represented by the following structural formula (Ina-1). -5-ene-2,3-diimineimine)phenyl}methane, anthracene represented by the following structural formula (Ina-2), Ν'-meta-phenylene-bis(co-propylbicyclo[2] ·2·1]heptene-2-eneimine), and N,Nf-hexaindolyl-bis(propylidenebicyclo) represented by the following structural formula (I-3) 2 2 1] 44 200813158 24843pif G-5-ene-2,3-dimethylimine). [Chem. 18]

<2. Heterocyclic compound used in the present invention> The heterocyclic compound used in the present invention has a selected from the group consisting of oxirane, oxetane, thiirane, and nitrogen. Aziridine, and one or more heterocyclic structures of the group consisting of 喔嗤 。. The above heterocyclic compound may be one compound having the above heterocyclic structure, or may be two or more kinds of compounds. One of the aforementioned heterocyclic compounds may have only one heterocyclic structure, and may have two or more heterocyclic structures. Further, one of the aforementioned heterocyclic compounds may have one of the above heterocyclic structures, but preferably has two or more of the above heterocyclic structures. Further, the heterocyclic compound may be a polymer having a heterocyclic structure in a side chain or a copolymer. A polymer having a heterocyclic structure in a side chain length, 45 200813158 24843pif J is a monomeric fish having a heterocyclic structure on a single bond having a material structure in a side chain, and may also be in a side material: in a side chain Two or more kinds of copolymerized heterocyclic structures of a monomer having a heterocyclic ring structure having a heterocyclic structure: ' may have a substance in a side chain. 4 kinds of precursors and monomers having a heterocyclic structure

'The description of the miscellaneous paving has (4) sub-AI liquid crystal alignment agent to inhibit the ion density production of the compound at 3 other places is not clear, but the reason for the excellent stability of a 埤 埤 ^ ^, ^ ^ ^ ^ is still a hetero atom and polyamine a compound of the heterocyclic ring in the heterocyclic structure of the compound; (part: when the film is a liquid crystal alignment film). Therefore, the above heterocyclic compound, for example, has an effect ^ The reaction of the atom with poly-aracine can cause the ring to have ethylene bromide (βxirane as a hetero compound), and the lower; the epoxy (w) heterocyclic ring has a spine ( Gxetane) as a heterocyclic structure, also known as "oxycyclobutane, also known as =_" as a heterocyclic compound heterocyclic compound (r. :, thioran (thllrane) compound), mainly having nitrogen and hydrogen A pyridine == a heterocyclic compound (hereinafter referred to as a yazmdme compound) as a heterocyclic structure, and a heterocyclic compound mainly having a ruthenium (hereinafter, also referred to as ". evil (four) compound" 乂The solvent for dissolving the polylysine used in the present invention or its derivative 46 200813158 24843pif organism is soluble. Examples of the oxetane compound include bis[(3-ethyl-3-epoxypropenylmethoxy)methyl]benzene and bis[(3_ethyl_3_epoxy). Propane methoxy)nonylphenyl]methane, bis[(3_ethyl_3_epoxypropenyl methoxy)methylphenyl]-, bis[(3-ethyl-3-epoxy) Propane methoxy)methylphenyl]propane, bis[(3-ethyl-3-epoxypropenyl methoxy)methylphenyl]anthracene, bis[(3_ethyl propylene oxide methoxy) Methylphenyl]-, bis[(3•ethyl_3_epoxypropenyloxy)methylphenyl;]hexafluoropropane, triethyl_3_epoxypropyl methoxy Methyl) is stupid, and tetra[(3-ethyl 1 epoxidized methoxy) decyl] benzene and the like. Other examples include oligomers and polymers having an oxypropylene group. Examples of the thiirane compound include phenyl glycidyl ether, butyl glycidyl group, and 3, 3, 3 - 3 according to the method described in JOrg. Chem., 28, 229 (1963). Fluoromethyl oxidation _, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, guanidinium hydrazide, (nonafluoro-N-butyl epoxide, perfluoroethyl glycidyl bond, Epoxy chloropropene, epoxy bromide, N,N-diglycidyl aniline, and 3·[2_(Wangfluorohexyl)ethoxy]_ι, 2_epoxypropene, ethylene glycol Fine, polyethylene glycol diglycidyl ether, propylene glycol dicondensate oil, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl, -6, diol Diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, and 3-(anthracene, Ν-diglycidyl)aminopropyltrimethoxydecane 1,3,5,6_tetraglycidyl 2,4-hexanediol, N,RN,,Nl tetraglycidyl 47 200813158 24843pif = Diphenylene diamine, U·double (N N-diglycidylmethyl)cyclohexane, n,w,n', glycidyl diaminodiphenylcarbamate, and HN-dil-v'glycidyl)aminopropyl In the case of the base, the water glyceryl group is substituted with sulfur, and the glycidol is substituted with a compound of the ethylene sulfide group. The aziridine compound may, for example, be 2, 4, 6 or 2 (1 虱 虱 疋 ))-ι, 3, 5 - 2 . Qin, ω_Aziridine-based propionic acid, bis-hydrazinyl heptanol, vinegar: 2,4,6·tris(2-indolyl-1_azepine), ^·triazine, 2,4 ,6-tris(2·^-based-=propane)_], 3,5-triazine, 4,4ι_bis (vinyl sulfite-based amine)-based decane, double (2_B丨_丨_aziridine group) stupid-^·dimethylamine, tris(2-ethyl-1-aziridine)benzene_U,5-tridecylamine, bis(2-ethyl)丨-aziridine) decanoic acid decylamine, 1,6-bis(vinyliminocarbonylaminoalkane, 2,4-diethylidene hydrazine, Ulcarbonyl-double-stranded ethyl Amines ", polyarylene-diethylurea (C2~C4), and Ν,Ν,-bis (4,6-di-extension-ethyl]--------- -yl) hexamethylene monoamine, etc. Other examples include oligomers and polymers having an aziridine group. As the oxazoline compound, 2,2'-double (2-oxo) Zolinium), 丨2 4_bis(2-oxazolinyl-2-)benzene, 4-furan-2-ylmethylenephenyl_4;^vowacean, 1,4_bis (4,5_ Dihydro-2-oxazolyl)benzene, 1,3_bis(4,5-dihydro-^-wodoyl)benzene, 2,3-bis(4)isopropenyl-2-oxazoline-1-yl) Alkane, 2, 2, _ double _4_ fluorenyl-2- sigma, 2,6 - Bis(isopropyl sitin-2-yl) oxime. Ding, 22, isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenylene), 2,2l methylene bis ( 4-tert-butyl-2-indolyl), and 2 2,_methylenebis(4-phenyl-2-oxazoline) and the like. Other examples include XK compounds and oligomers having a ketone base such as 48 200813158 24843pif (trade name: manufactured by Nippon Shokubai Co., Ltd.). Decrease the compound of 6-6, for example, what is the glycidyl group of the glycidyl group = the compound of the formula, the oxirane compound of the group 1 , the glycidyl compound, the 11% oxyethylene compound, the glycidylamine type A compound, a heterocyclic epoxy-acetate compound, an acrylic compound containing an ethylene oxide, a decane-type oxirane compound, or the like.

As a commercially available product of a glycidyl ether type oxirane compound, for example, Epikote 100, Ep彳kote 10〇2, Epikote 1003, Epikote 1004, Epikote l〇〇7, Epikote 1009, Epikote 1010 (Yuka) Shell

Epoxy (manufactured by Epoxy Co., Ltd.) and Epikote 8〇7 (manufactured by Yuka Shell Ep〇Xy Co., Ltd.) as a commercial product of a fatty ring-shaped epoxy epethane compound, such as CY

175, CY-177, CY-179 (manufactured by CIBA-GEIGY Co., Ltd.), ERL-4234, ERL-4299, ERL-4221, and 4206 (manufactured by UCC·Company); as a glycidyl ester type oxirane compound For sale, for example: シa — 夕, 彳 508 (Showa Denko (share) system), AralditCY 182,

Araldit CY — 192, Araldit CY — 184 (CIBA – GEIGY), EPICL0N 200, EPICL0N 400 (Dainippon Ink), Epikote 871, Epikote 872 (Yuka Shell Epoxy), ED — 5661, ED — 5662 (made by Celanese Coating), as a glycidylamine-type oxirane compound, for example, tetraglycidyldiaminediphenylmethane, triglycidyl-p-aminophenol, triple-shrinkage Glyceryl m-amino phenol, diglycidyl aniline, diglycidyl aniline, diglycidyl isophthalonitrile diamine, diglycidyl tribromoaniline, 49 200813158 24843pif diglycidyl bisamine Methylcyclohexane; commercially available as a heterocyclic oxirane compound, such as Araldit PT81® (CIBA – manufactured by GEIGY),

Epikote RXE — 15 (manufactured by Yuka Shell Epoxy Co., Ltd.) and epiteC (manufactured by Seiko Chemical Co., Ltd.); as an acrylic compound containing an oxirane group, radical polymerizable having an oxirane group The compound is obtained by radical polymerization of the compound alone and/or together with other radically polymerizable compounds in a solvent. Examples of the free silk compound having an epoxy 6 filament include, for example, water glycidyl ester, f-based acrylic acid-deficient dioleyl group, α-ethyl acrylate glycidyl ester, and α-n-propyl group. Acrylic glyceryl, α-n-butyl acrylate glycidyl ester, acrylic acid _3, oxo oxy butyl ester, methacrylic acid _3, 4 epoxide butyl ester, acrylic acid -6, 'ring, Base Day, methacrylic acid _6,7_epoxyhexyl ester, heart ethene _6,7_ = hexyl ester, Ν-[4_(2,3_epoxypropoxy)_3,5_ Dimethyl] propylene ΐ Ν [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ Most of them are polymers, but the epoxy ethene compound used in the present invention is not classified into two types. For example, it is also possible to use a divergent water such as a double or a double F, and a low molecular weight body such as a nightingale. Among them, in the case of a low molecular weight body, there is a possibility of enthalpy, and therefore a high molecular weight body is preferred. The oil is a ^^ type % oxyethylene compound, for example, (3, shrinkage) Glycyrrhizin , (3' glycidoxypropyl) decyl di, 2-(3,4 iron cyclohexyl) ethyl trimethoxy Wei, 5,6- hexylhexyl triethoxy Wei, glycidoxypropyl) Dimethylethylene 50 200813158 Oxydecane, (3-glycidoxypropyl)decyldiethoxydecane, and the like. In order to make the effect of the oxirane group remarkable, a catalyst can also be added to the epoxy ethene compound used in the present invention. Examples of the co-catalyst include, for example, σ ratio 17 each, taste saliva, 嗤 嗤, 啦 12 定, 吼 azine, mouth σ 、, 丨 朵 朵, 嗤, benzoquinone taste 17 sitting, heterotrimerization Cyanate and the like. Among these, 2-indole base rice, 2-ethyl-4-mercapto 1:7 m hydrazine, 2-17-base azole, 4-methyl-2-phenylimidazole, 1- Benzyl-2-mercaptoimidazole, 2-ethyl-4-indenyl-1, (2'-nitroethyl) hydroxy sylylene, 2-ethyl-4- fluorenyl-1-[2' -(3'',5?'-February Anji Sansyl) Ethyl] sigma sputum, awkward side / sitting and waiting 17 meters 嗤彳 hall creatures is appropriate. These catalysts may be used singly or in combination of two or more kinds. In general, it is preferably used in a proportion of 0.01 to 10 parts by weight based on the total amount of the oxirane compound (in terms of the total amount). The oxazine compound to be used in the present invention may, for example, be a compound represented by the following formulas (a) to (f), but is not particularly limited to these compounds.

51 200813158 24843pif In the general formulae (a), (b), (c), (d), (e), (f), r]&r2/ respectively represent an organic group having a carbon number of 1 to 10, and R3 to R6; Separately -&2, + = ~ a gas-free or stone-reverse number 1 to 6 hydrocarbon group, X represents a single bond, -0-, each, s!, w Λ -CO- Λ -CONH-, -NHCO- , -C(CH3)2-, -C(CF3)2...(CH), -S-, -CO-, -C(CH3)2-, -C(CF3)2_4, carbon number 丨~3 alkyl. In the general formulae (a), (b), (c), (d), (e), (f), the hydrogen bonded to the benzene ring or the ring may be independently substituted into _F, _CH 〇Η , -S〇3H, or -ί>〇3Η2. -0-(CH2)m-0·, or -S-(CH2)m-S-, m represents n _ number m. In the 'other' formula (〇, (f), Y independently represents a single bond _〇_,

Further, the oxazine compound to be used in the present invention comprises a filament having a stimulating structure in a side chain and a polymer, and a azine pyrimide and a polymer in the domain. It is represented by the general formula (a). The oxazine compound can be, for example, a compound of the following formula (4). [Chem. 20]

(4)) (a, 2) In the general formula (a~2), only 1 is a carbon number of 1 to 20, and the base of the carbon is 1 to 3G, and 52 is the base of the 200813158 24843pif. b) The oxazine compound to be represented, for example, is a oxazine compound represented by the following structural formula and formula. [Chem. 21]

(iv)) {5-2}

53 200813158 24843pif In the general formulae (b-2), (b-8), (b-10), R1 is preferably an alkyl group independently having a carbon number of 1 to 30, more preferably a carbon number of 1~ 20 alkyl groups. The oxazine compound represented by the formula (c) includes, for example, an oxazine compound represented by the following structural formula and formula. [化22]

54 200813158 24843pif

(c-10)

{0-14) In the general formulae (c-2), (c-4), (c-6), (c-8), (c-10), (c-12), R1 is preferably carbon. The number of the alkyl groups of 1 to 30 is more preferably a carbon number of 1 to 20. The oxazine compound represented by the formula (d) is, for example, an oxazine compound represented by the following structural formula. [Chem. 23] 55 200813158 24843pif

(d-7)

(d_8)

The oxazine represented by the formula (e) is, for example, a sigrozine compound represented by the following formula. 56 200813158 24843pif [Chem. 24]

The σ oxime compound represented by the configuration. [Chem. 25]

57 200813158 24843pif

Among these, it is better to mention: structural formula (b-1), (c-1), (c-3), (c-5), (c-7), (c-9), D-1)~(d-6), (e-3), (e-4), (f-2)~(f-4) Qin Qinhe 58 200813158 24843pif 0W oxazine compound, For example, it can be produced by the same method as the method described in Japanese Patent Laid-Open No. Hei 11-12258, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. <3. Polylysine or derivative thereof used in the present invention> Polylysine or a derivative thereof used in the present invention is prepared by dissolving a liquid crystal alignment agent described later in a solvent. When the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later, it is a component which can form a liquid crystal alignment enthalpy in the form of a polyimide. Examples of such a polyamic acid or a derivative thereof include L acid, soluble polyamine, polygilic acid, and polyamic acid. More specifically, (1) all of the amine groups of poly-proline are dehydrated and reacted (four) (iv) imine, (2) part of the polyether amine formed by partial dehydration ring closure reaction, (3) polydecylamine The acidity is changed by the specific purpose of the poly-acid §, (4) part of the acid dianhydride contained in the acid two is replaced by organic two sincere and reversal (four) material (four), correct (5) to make the poly ir Part or all of the dehydration ring-closing reaction, the product ': is, the component of the component, or two of them: two to describe the amino acid or its derivative, compared to #～B The amine is '(4) is the polyamine derivative obtained by the acid component ^ i ± knife-^ reaction. In the J invention, such a polyamine can be used. The poly-proline or a derivative thereof can be obtained by a reaction. The fourth invention of the present invention can be used; the use of 59 200813158 24843pif for the above four readings, but the portion of the four dianhydrides can also be replaced by the second thief. Here, the ratio of the two fine items to the four-two-two technique is preferably 10 mol% or less. As the diamine of the present invention, one type or two or more kinds of diamines may be used, but the - part of the diamine may be substituted with a monoamine. Here, it is preferred that the ratio of the monoamine to the diamine is 1 〇 mol% or less.

The above four ortho-acid dianhydrides can be used arbitrarily for one or two or more compounds. When two or more tetrahedral dianhydrides are used, it is preferred that the aromatic succinic acid is used as the bismuth component of the acid, the anti-family tetrahydrous dianhydride, and the alicyclic _acid two or two. As the B component of the acid. These tetra-di-I can use one or two or more compounds, respectively. Further, in the case where the poly-acid of the present invention is used as a component of the liquid crystal alignment agent, it is preferred that the ruthenium 4 is soluble in the form of the solvent g. In order to prepare the soluble substance for the polyamic acid, it is preferred to appropriately select the tetracarboxylic dianhydride used as the acid component. Here, the aromatic anhydride which is used as the component A of the acid, for example, may be exemplified by the acid dianhydride represented by the HX undercut structures (1) to (18). The following aromatic tetrazins are more preferably represented by the structural formulae (1), (7), (5), (4), (7), and preferably by the acid formula represented by the structural formula. No pyromellitic dianhydride 0 [Chem. 26]

(3) 60 200813158 24843pif

In addition, as the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride which are used as the component B of the acid, for example, an acid represented by the following structural formula (19) 61 200813158 24843pif (67,) can be specifically exemplified. Diacid anhydride. [化27]

Q Ο Ο CH30

(20) CH3 CH; tri 〇 m CH3 CH {22}

β b (23)

Ch3 b (21)

G

O

0 k, ” 1 rr<〇厂 0 0 0 y (32) (33) (34) 62 200813158 24843pif

(3S) (39) (40) (41)

(42)

(46) (45)

63 200813158 24843pif

Among the above tetracarboxylic dianhydrides, acid dianhydrides represented by structural formulas (19) to (39) and (49) are preferably mentioned, and structural formula 64 200813158 24843pif (19) is more preferable. The acid dianhydride represented by (23), (25), (35) to (37), (39), (44), and (49) is particularly preferably represented by the structural formula (19). , 2,3,4-cyclobutane tetracarboxylic dianhydride. Further, in order to form the polylysine of the present invention or a derivative thereof into a solvent-soluble polyimine, it is preferred to use structural formulas (24), (35) to (44), (49). Acid dianhydride represented by (50), (53) and (6). In the tetracarboxylic acid monoanhydride of the present invention, the tetracarboxylic dianhydride represented by the structural formula (丨) to (67) may be used alone, or two or more of them may be used in combination. (Using aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride (especially good is tetraphenyl dianhydride, 1,2,3,4-cyclobutane) a liquid crystal alignment film which is formed by a liquid crystal alignment agent comprising polyamic acid synthesized by the tetrazoic acid dianhydride of the present invention, which is capable of imparting a liquid crystal containing the liquid crystal alignment film. The display element has a particularly good ion density. Further, the tetracarboxylic dianhydride of the present invention may be used in addition to the tetracarboxylic acid diterpene other than the tetracarboxylic dianhydride represented by the structural formulas (1) to (67). The I-tetracarboxylic dianhydride is arbitrary, and, for example, a tetrabasic acid dianhydride having a side chain structure, and the following liquid crystal alignment film having a side chain structure of four resorcinic dianhydrides may be used. A pretilt angle in a liquid crystal display element comprising the liquid crystal alignment film which is formed using a liquid crystal alignment agent comprising polylysine synthesized by the four resorcinic acid anhydrides of the present invention. The tetracarboxylic dianhydride of the chain structure is not particularly limited, but in the present invention, A compound having a steroid skeleton represented by the following structural formulas (68) and (69) is preferably used. 65 200813158 24843pif [Chem. 28]

The aforementioned other tetracarboxylic acid which can be used in the acid tetracarboxylic dianhydride

The four-ship dianhydride with a side chain structure in the front , can also have other various forms of tetracarboxylic acid and other four (four) two pores in the square of the acid/bright purpose. It can be used alone or two. The above combination is used. The progress of the above reaction proceeds, so that the molecular weight of the obtained polymer (polylactoic acid) can be easily controlled. The ratio of the carboxylic anhydride to the tetracarboxylic anhydride may not be impaired, and the portion of the tetracarboxylic dianhydride used in the tetracarboxylic dianhydride of the present invention may be substituted with the carboxylic acid anhydride. By substituting a portion of the tetracarboxylic dianhydride to a carboxylic acid anhydride, the termination of the polymerization reaction can be caused, and the effect of 66 200813158 24843 pif can be suppressed, but as a standard, it is preferably set as the total tetracarboxylic acid. The amount of the second wild is ΙΟιπο〗% below. As described above, the polyphthalic acid contained in the liquid crystal alignment agent of the present invention is a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine. The diamine used in the present invention may be arbitrarily selected from one or two or more compounds. As the diamine, for example, a linear diamine can be used alone as a quinone component, and = a diamine of the component A and a bivalent having a side chain structure as a component b can be used. In the case where two or more diamines are used, for example, it is preferred that the amine is used as the component A of the amine, and the component B having the reversed structure as the amine is used. For these diamines, one or more compounds may be used separately. Μ 构 之 ( ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν The diamine represented by the formula (I)~ is exemplified. 67 200813158 24843pif H^N one

{〇 (It) (10) 〇V) (V) (Vf) (VI!) nh2 In the general formula (I), A1 represents _(CH2)m-. Here, m represents an integer of 1 to 12. Further, in the general formulae (IH), (V), and (YU), A1 independently represents a single bond, -0-, -S-, _S_S---S02-, -CO·, -CONH-, _NHCO-, respectively. , -C(CH3)2_, -C(CF3)2_, _(CH2)m-, -0-(CH2)m_0-, or -S-(CH2)m_S-. Here ni independently represents an integer from 1 to 12. Further, in the formula (VI), A2 independently represents a single bond, -0-, -S-, _CO-, -C(CH3)2-, -C(CF3)2- or a carbon number of 1 to 6 alkyl. Further, the hydrogen bonded to the cyclohexane ring or the benzene ring in the formula (Π) to (W) may be independently substituted with -F, _CH3'-OH, -CO〇H, -S03H, - Ρ03Η2, benzyl or 4-hydroxyl group. The diamine represented by the formula (I) is, for example, a diamine represented by the structure (I-1) to (I-4) of the group 68 200813158 24843pif. H2M(CH2)2MH2 H2M(CH2}4NH2H2N(CH2)6NH2 h2m(ch2)12nh2 (Μ) _ (I-3) {M} As a diamine represented by the formula (Π), for example The diamine represented by the structural formula (π - 1) and (π - 2) can be mentioned.

Η2Ν-<^)-ΝΗ2 Η2Ν 阙 阙 The diamine represented by the formula (m) is, for example, a diamine represented by the structural formula (m-1) to (m-3). [化32]

The diamine represented by the formula (IV) is, for example, a diamine represented by the structural formulae (IV-1) to (IV-16). 69 200813158 24843pif [Chem. 33] ^~~NH2 (IV-1) H2N—*NH2 (lV-2)

H2N

(IV-3)

HOOC

OH

H2r, _ (chest)

HO h2n— »—nh2 (JV-7)

COOH

N2rr, called (fV_8) / H2M1 —nh2

〒03H2 ho3s h2nx ^ 'NH2 (IV-12) (JV-9) (IV-1t)

The diamine represented by the formula (V) is, for example, a diamine represented by the structural formula (V-1) to (V-34). 70 200813158 24843pif [化 34] Η#—NH2 H2N (V-1)

-NH2 (V-2) (V»3)

(V-7) (V-6) /GH3 —/^X 邮\ NH2 Η2ΝΛ_^ν^ΝΗ2 QH3 - (V«9)

(ν·12) , 〇, h2nh; v /rh^/-nh2 h2n^ /r^v^vN^ η2ι^γ^τ_υ ynh2 (V-13) (V-14) {V-15) _·~ 〇"〇ν〇χ〇^_ (V^16) (V-17) 71 200813158 24843pif Η2Ν· (V-18)

IsIH2 h2n-

(XA19)

H2N (V-20) (V, 21)

HaN NH2 is called (\A23) (V^22) h2n-

(V*24) Delete 2 " '\^ΙΙ , \ // (V-25)

(V-26)

H2N (V-27)

(V-31) (ν·32)

The diamine represented by the formula (VI) is, for example, a diamine represented by the formula (vi-1) to (VI-6) of the formula 72 200813158 24843pif. [化35]

(Vi-2) (VM)

(νμδ) {Vl-δ) The diamine represented by the formula (VH) is, for example, a diamine represented by the structural formula (W-1) to (YU-16). [化36]

(Vikl) (VH-2) (Vi 1-3} h3c ch3 Η2Ν vy" (Vil-5)

〇AU6) 73 200813158 24843pif

H2H

NH2 (VII-7)

NH2 %N (V|j«9)

Nh2 (Vli-8)

(ViP10) _*41) (VH-12)

(VU-IS) (VIM 6) Among these, the structural formulae (IV-1) to (IV-5), (IV-15), (IV-16), (Vl)~(( V-12), (V-26), (V-27), (V-31), (V-33), (VI-1), (VI-2), (VI v-6), (YU — 1) The diamine represented by (W-5) is preferably exemplified by structural formulae (IV-1), (IV-2), (rv-15), (IV-16), (v). 1) a diamine represented by (V-12), (V-33), (W-2). The diamine of the present invention may be used singly as shown in the above formula (I) to (W). The amine may be used in combination of two or more kinds. The molar ratio of the diamine represented by the above formulas (I) to (W) in the diamine of the present invention may be selected according to the above formula (I)~ The structure of the diamine represented by (W) and the desired ion density are adjusted, preferably 74 200813158 24843 pif 疋 1 to 100%, more preferably 5 to 80 〇 / 以 based on the total amount of the diamine. As before, the diamine of the present invention may be (tetra)-diamine', but especially in the case of a VA type liquid crystal display element, the element ^sTM bribe (four) in order to obtain a large turn / ρΪ afe) of applications, it is preferable that a side chain having a structure of β 2 to the amine component.扪 扪 胺 胺 作

In the present specification, a diamine having a side bond structure, a substituent which is intended to link two amine groups, is used as a main chain, and the self-bonding can be expressed as a TM angle (-_ has one of "#. A bribe with a side chain structure should provide: a poly-chitoic acid or a polyimine (a branched poly- or a branched (tetra) imine) having a side chain group relative to the polymer backbone: The liquid crystal alignment film comprising a liquid crystal alignment agent comprising a polyacrylamide having a side chain group with respect to a polymer main chain, which can increase a pretilt angle in the liquid crystal display element. In this case, for example, the above-mentioned Patent Document 1 (Japanese Patent Laid-Open Publication No. No. 193345). Therefore, the side chain of the diamine having a side chain structure can be adjusted according to the required pretilt angle. For example, the number of carbon atoms in the side chain is preferably 3 or more. Specific examples thereof include (1) a phenyl group which may have a substituent, and a cyclohexyl group which may have a substituent. a phenyl group, a bis(cyclohexyl)phenyl group which may have a substituent, or a carbonyl group or a dilute group having a carbon number of 3 or more Or a block group, (2) a phenoxy group which may have a substituent, a cyclohexyloxy group which may have a substituent, a bis(cyclohexyl)oxy group which may have a substituent, and a stupid group which may have a substituent 75 200813158 24843pif base ring An oxy group, a cyclohexylphenoxy group which may have a substituent, an alkoxy group having 3 or more carbon atoms, an alkenyloxy group or an alkynyloxy group, (3) a phenylcarbonyl group, or an alkylcarbonyl group having a carbon number of 3 or more , alkenylcarbonyl or alkynyl, (4) phenyl phenyloxy, or a carbyloxy group having a carbon number of 3 or more, a thioloxy group or a fast phenyloxy group, (5) a benzyloxy group which may have a substituent, a cyclohexyloxycarbonyl group which may have a substituent, a bis(cyclohexyl)oxycarbonyl group which may have a substituent, a bis(cyclohexyl)phenyloxy group which may have a substituent A cyclyl group, a cyclohexyl bis(phenyl)oxycarbonyl group which may have a substituent, an alkyloxycarbonyl group having a carbon number of 3 or more, an alkenyloxy group or a fast oxy group, (6) benzene a arylaminocarbonyl group, or an alkylamino group having a carbon number of 3 or more, an alkenylaminocarbonyl group or an alkynylaminocarbonyl group, (7) a ring having 3 or more carbon atoms An alkyl group, (8) a cyclohexylalkyl group which may have a substituent, a phenylalkyl group which may have a substituent, a bis(cyclohexyl)alkyl group which may have a substituent, a cyclohexylbenzene which may have a substituent An alkylene group, a bis(cyclohexyl)phenyl extended group which may have a substituent, a phenylalkyloxy group which may have a substituent, an alkylphenyloxycarbonyl group, or an alkylbiphenyloxy group, (9) by: :: a carboxyl group, a fluorine-substituted alkyl group, or an alkyl group substituted with an alkoxy group, or a cyclohexyl group, and (10) two or more benzene rings or a cyclohexane ring bonded by a single bond, or Alkyl group bonded via -0-, -COO-, -OCO-, _C0NH_ or a C 1 to 3 alkyl group, a monofluoro substituted alkyl group, or a ring substituted by an alkoxy group. 200813158 24843pif Collective group Further, the base having a steroid skeleton or the like is not limited thereto. Examples of the "substituent" include an alkyl group, an alkoxy group, or an alkoxyalkyl group. Alternatively, bis(cyclohexyl) or bis(stupyl) may be interrupted by an alkyl group. Further, in the present specification, in the case of "alkyl group", "alkenyl group" or "alkynyl group", it may be in the form of a line or a branch. Specific examples of the diamine having a side chain structure used in the present invention include diamines represented by the following formulas (Μ) to (Xu). [化37]

In the general formula (VI), Ri represents a single bond, κ〇...c〇〇_, _〇c〇_, _CON=-, :CH2〇...CF2a or <CH2)e, and e represents an integer of Bu6: R It is a group having a steroid skeleton, or a phenyl group having a base carbon number of 1 to 3 Å represented by the following formula: or a phenyl group; and when the carbon content of the above-mentioned stretched yarn and the yarn is 2 or more _CH2_ can also be independently Ο 01-〇1- or _(^_substitution (where oxygen is discontinuous), followed by the thief, methyl, methoxy-fluoromethoxy, - gas-milk-based or trifluoromethoxy substituted, but chick _r1_r2 represents the nodal group ^ Ί η Ύ Λ Λ 0 77 200813158 24843pif [化38]

〇c) an alkyl group having 1 to 30 carbon atoms; R5 independently represents a single bond; in the general formula (8), R3 independently represents hydrogen or a methyl group; r4 represents a gas CO- or a pass, (X) a towel, and R3 independently represents money. Or a base; to the table = stone difference W30 (four) base; R5 independently represents a single bond, _c〇 or Ϊ ^ ^. And R? independently represent hydrogen, carbon number 1 to (four) filament, [Chem. 39]

R 10 d R11 H2N〇i-

\ h12

(ΧΙΪ) 78 200813158 24843pif In the general formula (XI), 'R8' represents hydrogen or a calcined group having 1 to 3 carbon atoms, and any of the above-mentioned alkyl groups having 2 or more carbon atoms may be independently _〇_ , -CH=CH Cheng-CEC-substitution (wherein oxygen is discontinuous); R9 independently represents -0- or alkylene with a carbon number i~6; ring A represents 1,4-phenylene or M-ring Extending the base; a means 〇 or 1; b means 〇, 1 or 2; c independently represents 0 or 1. In the general formula (XH), 'R1G represents an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having a carbon number of 3% to 5%; Rn represents hydrogen, a alkyl group having 1 to 30 carbon atoms, or a carbon number of 1 to 30. The monofluorinated alkyl group; R12 independently represents _〇_ or a carbon number of 1 to 6; and d independently represents 〇 or 1. [40]

In the formula (ΧΠ), Ri3, RM&R]5 each independently represent a single bond, ...COO...OCO...c〇NH_, an alkylene group of carbon number 4, an alkyloxy group having a carbon number of 1 to 3 ( Wherein the oxygen is discontinuous, or the carbon number is 1 to 3 (the towel oxygen* is continuous); Rn independently represents hydrogen, fluorine or sulfhydryl; R18 represents hydrogen, fluorine, chlorine, sulfhydryl, carbon Alkoxy group having a number of 1 to 3 fluorene, alkoxyalkyltrifluoroindolyl having 2 to 3 fluorene, difluoromethyl, trifluoromethyl, monofluoromethoxy , difluoromethoxy or trifluorodecyloxy; any of the above-mentioned burnt beauty, hospital negative enthalpy, and any of the oxygen-burning ship bases having a carbon number of 2 or more may also be exemplified by the following formula (XIV) The substituents are represented; ring B and ring C each independently represent a 1,4-phenylene group or a 1,4-cyclohexyl group; f, g and h each independently represent an integer of 0 to 4; i, j and k each independently represents an integer of 0 to 3, and the total of these values is 1 or more; 1 and m each independently represent 1 or 2. [化41]

In the formula (XIV), R19, R2G, R21 and R22 each independently represent a carbon group having 1 to 10 carbon atoms or a phenyl group, and η represents an integer of 1 to 100. Further, in the formula (Κ), hydrogen bonded to the carbon forming the steroid skeleton may be independently substituted with -CH3. The diamine represented by the formula (M) may, for example, be a diamine represented by the following general formula or structural formula (W-1) to (M-43). [化42] 80 200813158 24843pif

(V1IM) {Vlll-2) (Viii-3)

(vm-6)

In the general formulae (M-1) to (M-11), R23 preferably represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably a carbon number of 5 to 2 5 An alkyl group having a burning group or a carbon number of 5 to 2 5 . Further, R24 preferably represents a burnt group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. 81 200813158 24843pif [化 43]

(V\\\A2) (VHM3) R25 / 0=0

(_-14) , R26 ? (VfiMS) (VIIM7)

In the formula (12) to (M-15), R25 preferably represents an alkyl group having 4 to 30 carbon atoms, more preferably an alkyl group having 6 to 25 carbon atoms. In the formula (Μ-16) and (Μ-17), R26 preferably represents an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms. [化44] 82 200813158 24843pif

°Or27 H2N

.{VIIi-19) {Vlll-tS}

(Vlll-20)

H2n

(Vim22)

_ 卜 23)

H2H

〇

>27 h2n (V!lh24)

(Vili-25)

H2n H2M o

►28 (VI1I-27)

(Vll^28) 83 200813158 24843pif f.

(VIII-29) (10) Bu 30)

O.

?28 (VHi~32)

H2N

R27

H2N (VHI-3S)

N

‘R28

H2N

Ch3 ch3 Si-O-Si-R27 CH3 ch3 In the formula (M-18)~(M-37), R27 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. The group preferably represents an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. Further, -Η, -F, an alkyl group having 1 to 30 carbon atoms, and an alkane 84 having a carbon number of 1 to 30 are preferably represented. 200813158 24843pif oxy group, -CN, -OCH2F, -OCHF2 or -OCF3, more preferably It represents an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. [化45]

\

Among these, a diamine represented by the formula (M-1) to (M-11) is preferably mentioned. More preferably, the diamines represented by the formulae (M-2), (M-4), (Μ 85 200813158 24843pif-5) and (M-6) are mentioned. In the above formula (IX), it is preferred that one of the two "NH2-Ph-R5-〇-" is bonded to the 3-position of the steroid skeleton, and the other is bonded to the 6-position. Further, it is preferred that the two amine groups are bonded to the phenyl ring carbon, respectively, and the bonding position with respect to R5 is bonded to the meta or para position. As the diamine represented by the formula (IX), for example, a diamine represented by the structural formula (K-1) to (IX-4) can be obtained. [Chem. 46]

In the above formula (X), two "NH2_(R7-)Ph-R5-0-" are bonded to the carbon of the phenyl ring, respectively, but preferably, the carbon bonded to the steroid skeleton For the meta or alignment barrier. Further, two amine groups are respectively 86 200813158 24843pif bonded to a phenyl ring carbon, but preferably, it is bonded to the meta or para position relative to R5. The diamine represented by the formula (X) may, for example, be a diamine represented by the structural formula (X-1) to (X-8). [化47] 87 200813158 24843pif

88 200813158 24843pif

Side 2 89 200813158 24843pif

In the above formula (XI), the two amine groups are bonded to the carbon of the phenyl ring, respectively, and it is preferred to bond to the meta or para position with respect to R9. The diamine represented by the formula (XI) may, for example, be a diamine represented by the general formula (XI-1) to (XI-8). [化48] R29 R29

90 200813158 24843pif

R29

Nh2 R30 h2m

r3G

NH2 91 200813158 24843pif

In the general formula (X[-1] to (XI-3), R29 preferably represents _H, an alkyl group having 1 to 30 carbon atoms; and in the formula (X!-4) to (XI-8), r30 It is better to represent the base of Η and soil with a number of 1 to 20.

In the 刖 刖 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The diamine represented by the formula (Μ), the diamine represented by the formula (-1) to (Μ-3). Give a general formula (view 49)

(ΧΙΜ)

(ΧΙΙ-2) 92 200813158 24843pif r32

(X^3) in the general formula (welcome) 6~2〇 of the burning group, only 32 志, force, RJ] better represents the carbon number of the present invention diamine = _H or carbon number 1 ~ (four) Burning base. The H species shown are a brief description of the diamines having a side chain structure of the general formula () to (evil), and two or more kinds. The ratio of the dip of the diamine side chain structure of the present invention may be adjusted according to the selected one, preferably f, and a desired pretilt angle, and further, 疋1 to 1%%. Better is 10 to 100%. The diamine ί = diamine represented by the formula (1) to (f) side chain structure may be represented by the formula () to (view), for example, other diamines other than the oxime. Such other diamines are any of the fluorene-based diamines, the naphthalene-based diamines having a Qin structure, the rhythm (Μ) having a fluorene structure, and the diarrhea-based diamines having a sulphur-oxygen bond. Or a diamine having a side chain structure other than c. The following formula [υΓ糸-amine is not particularly limited], but a compound represented by [Chem. 50]) can be preferably used as the diamine of the present invention.

(XV) In the formula (XV), R and R"4 each independently represent a carbon number of 3~3 93 200813158 24843pif of an alkyl group or a phenyl group, and A3 independently represents a methylene group, a phenyl group or an alkyl group. Stretch phenyl. 1 represents an integer of 1 to 6, and m represents an integer of 1 to 1 。. Further, the other diamine is not limited to the above-mentioned alkoxy-based diamine. For example, a compound represented by the following formula (Γ) to (8,) can be preferably used as the diamine of the present invention. [化 51]

(8?) independently represent the alkyl group of the formula (Γ) to the number of 3 to 30. Further, the other diamines other than the ones used in the R35 and the diamine of the present invention, and the above-mentioned diamines are not limited to the above-mentioned alkoxynane-based diamines, and of course, the present invention has been achieved. Various other forms of diamines are also present within the scope of the purpose. Further, the other diamines may be used singly or in combination of two or more kinds. The diamine of the present invention can be imparted with a suitable pretiit angle by using a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention by appropriately selecting the kind of the diamine and the combination thereof. f

In the case of a VA type liquid crystal display element, ribs to 卯 are often required. The large pre-tilt angle of the left and right; the ambiguity of the OCB type liquid crystal display element requires that the TM right pre-existing in the TM type liquid crystal device: in the case of the STN type liquid crystal display element, a pretilt angle of about 3 to 1 常 is often required. In the case of an IPS type liquid crystal display element, a pretilt angle of about 〇~y is often required. Therefore, the liquid crystal alignment agent of the present invention can be suitably adjusted by using a diamine having a side chain structure, and can be applied to a liquid crystal display element of any sound type. 'α As described above, a part of the diamine used in the diamine of the present invention may be substituted with a monoamine. By substituting a portion of the diamine to a monoamine: the termination of the polymerization reaction proceeds, the progress of the previous reaction can be suppressed, so that the molecular weight of the obtained polymer (poly-acid) can be easily suppressed. The ratio of the mono-diamine to the diamine may be changed without impairing the effects of the present invention. As a standard, it is preferred to set the amount of the total amine to 10 mol% or less. The amine acid or derivative thereof of the present invention may have any weight average molecular weight. For the weight average molecular weight of the aforementioned polyaminic acid or its derivative! It is particularly limited, but in the case of being used as a component of a liquid crystal alignment agent, it is preferably 5x10 or more, more preferably ixi〇4 or more. The polyglycolic acid or a derivative thereof having a weight average molecular weight of 5 x 1 〇 3 or more does not evaporate in the step of the section: the night 曰 alignment film, and thus has a preferable physical property as a component of the liquid crystal alignment agent. Here, the weight average molecular weight of polyacrylic acid or a derivative thereof is determined by a gel permeation chromatography (GPC) method. For example, the obtained polydamine or its derivative is diluted with dimethyl decylamine (DMF) to form polyglycolic acid.

The concentration of the derivative is about 1 weight. /❶, using Chromatopac C~^ 孝制制制制), using DMF as a developing solvent and using gel permeation; the show is measured by the second analysis (GPC) method, and polystyrene conversion is performed to obtain a polyamine acid or a derivative thereof. The weight average molecular weight of the material. Further, in order to accurately measure the Gpc of polyacrylic acid and polyacrylic acid, 5, and the inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid, and lithium bromide or chlorinated di-inorganic salt are dissolved in the DMF solvent. The solvent is developed. The poly-proline or the derivative thereof of the present invention can be produced by a known method. For example, the reaction m having a raw material inlet, a nitrogen gas inlet, a thermometer, a mixer, and a condensation n is added to the formula ( 〗 〖) Two: or two or more of the diamines, depending on the situation, are selected from the group of: one or two or more kinds of diamines, and then added as needed or two or more, 隹I, :: 4) and the total amount of the total amount of tetradecanoic acid dianhydride, it is preferable to set the carboxylic anhydride to be added as needed. At this time, the total number of ears of the 'four month's tetracarboxylic dianhydride is approximately Etc 96 96 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 By heating to increase the reaction temperature (for example, 50 to 80 ° C), a polyglycine having a small molecular weight can also be obtained. The polyproline of the present invention is precipitated with a large amount of poor solvent, and then filtered. The solid fraction is completely separated from the solvent and analyzed by IR and NMR, thereby allowing it to be carried out. Further, the solid polylysine is decomposed by a strong alkali aqueous solution such as KOH or NaOH, and then extracted with an organic solvent, and analyzed by GC 'HPLC or GC-MS, whereby the monomers used can be identified. For the solution of the obtained polyamic acid, in order to adjust it to a desired viscosity, it may be diluted with a solvent and used. Further, the polylysine of the present invention is made into a poly-proline derivative. In the case of soluble polyimine, the polyproline solution can be used as an anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride as a dehydrating agent, and triethylamine, pyridine or triterpenoid as a dehydration ring-closing catalyst. A tertiary amine such as pyridine is obtained by carrying out a hydrazine imidization reaction at a temperature of 20 to 150° C. Alternatively, a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol or isopropanol and a glycol solvent) may be used. The polyamic acid is precipitated from the polyaminic acid solution, and the precipitated polylysine is dissolved in a solvent such as toluene or xylene, together with the same dehydrating agent and dehydration ring-closing catalyst as described above, at a temperature of 20醯iamine at ~150 °C In the above hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (mole ratio). The total amount of the two is better than that of 97 200813158 24843pif. The total molar amount of the acid dianhydride contained in the tetracarboxylic dianhydride used is from 1. 5 to 10 times the molar amount. The amount of the dehydrating agent and the amount of the catalyst can be adjusted by adjusting the chemical 醯 sub-face. And the reaction temperature and the reaction time, and the degree of imidization is controlled, and a part of the polyimine is obtained. The obtained polyimine is separated from the solvent, and the alkenyl group may be substituted in the solvent described later. The modifier of the Nadick acid ylide imine compound and at least one selected from the group consisting of the above heterocyclic compounds is used together as a liquid crystal alignment back, or may be added without being separated from the solvent. The modifier is used as a liquid crystal alignment agent to cause enthalpy. Further, as described above, a part of the acid dianhydride used in the tetracarboxylic dianhydride of the present invention may be substituted with an organic dicarboxylic acid. When the polydiamide of the present invention is produced using an organic dicarboxylic acid and a tetracarboxylic dianhydride, a polyamine amine oxime-1 amine copolymer can be obtained. Here, the ratio of the organic di-hypo-acid to the four-repulsive di-hepatic liver' may be within a range that does not impair the effects of the present invention, and is preferably 10 mol% or less as a standard. Further, the polyamidoquinone imine can be produced by chemically imidating the polyamine-polyamine copolymer. <4. Liquid crystal alignment agent of the present invention> The liquid crystal alignment agent of the present invention comprises the above alkenyl-substituted nadic acid acid imine compound, the above heterocyclic compound, and the aforementioned polyglycine or derivative thereof . The liquid crystal alignment agent of the present invention may further contain various additives contained in a usual liquid crystal alignment agent from the viewpoints of adjustment of physical properties such as viscosity, ease of availability, simplification of steps, and the like. 98 200813158 24843pif

The inclusion ratio of the alkenyl-substituted nadic acid-based compound of the modifier in the liquid crystal alignment agent is preferably a poly-acid or a property thereof per 1 part by weight of the liquid crystal formulation. In terms of A, _ parts by weight, more preferably 1 to 7 parts by weight, and even more than 50 parts by weight of I, I, as a liquid crystal age component light electrical touch long-term silent is better. The above-mentioned liquid crystal alignment agent of the present invention is stable in terms of the total amount, and it is Bugangqi: in terms of the total amount, it is better that the poly_ or its street is a (four) amount. More preferably, from 1 to 7 parts by weight, the aforementioned heterogeneous amount in the above heterocyclic compound depends on the decrease in the density of the liquid crystal alignment agent of the heterocyclic structure and the relationship of its diachronic increase, as described above. The performance of the above effects between the secret secrets is _. For the heart, the amount of the heterocyclic structure and the ethylene oxide oxime in the oxiranidated human compound in the liquid crystal alignment agent, in the case of ethylene oxide relative to poly-amic acid or its property ^ In the case of epoxy bake, it is preferred that the oxygen ring-containing compound in the agent contains denier::, 1:80% by weight. Liquid crystal alignment Cyclopentadiene structure conversion money ring = ‘(4) Τ Τ 中 Τ Τ 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其Preferably, it is 'in comparison with the thiirane compound of the octagonal 〇 / 〇. In the liquid crystal alignment agent, the thioform is converted into the sputum, and the bismuth sulphate in the bismuth The target is 0.1 to 80% by weight for poly-aracine or its derivative 99 200813158 24843pif. In addition, the liquid is woven in the heart of ~80 weight: heart: into the 1 mesh for poly-proline or its derivative is 〇. 〗 〖 In the liquid in the daily aligning agent oxazoline compound content, of: in the compound The salivary structure is changed for the poly-proline or its derivative is Qi~8 Miao^f f, its street bio-small Γ~δ(^=(四)岐, relative to the (tetra)amine or otherwise, contained in the heterocyclic compound In the case of two kinds, the ratio of each heterocyclic ring structure in the heterocyclic ring shape of the liquid crystal alignment agent is determined. *Dick generation in the Chening 5, =r?=:r diachronic two pieces of the ratio ##'s secret is αΐ ~' More preferably 〇5~5 The polyaminic acid of the present invention or a derivative thereof, or a derivative thereof. For example, if it is a poly-proline, the oxime component or the quinone component of the amine acid is The polyamine acid obtained by the acid component of the above-mentioned amine, the hydrazine component of the acid, the sulfonium component of the acid, the acid component of the eight-component or the component B, and the filament of the B-line and the sulfonamide. ^There is the opposite of the tyrosine acid, and the A component of the aforementioned acid and the second pass

Composition and component B reacted to the agglomeration of Wei (tetra)amine A 100 200813158 24843pif

c The content of polyphthalic acid or a derivative thereof in the liquid crystal alignment agent of the present invention can be appropriately selected depending on the coating method in which the liquid crystal alignment agent is applied onto the substrate. For example, a printing machine used in a manufacturing process of a general liquid crystal display element (including an offset priter and an ink jet printer; hereinafter, simply referred to as "printer") is used in a liquid crystal alignment agent. The content of the acid or its derivative is preferably from 0.5 to 30% by weight, more preferably from 1 to 15% by weight based on the total amount, and can be appropriately adjusted depending on the relationship with the viscosity of the liquid crystal alignment agent. The solvent used in the present invention broadly comprises a solvent commonly used in the production steps and uses of polymolecular acid, soluble χκ酉&imine, and xjx &&amine amine imine; Make appropriate choices according to the purpose of use. The solvent is preferably (1) an aprotic polar organic solvent which is soluble in polylysine and a soluble polyimine, and (2) which is intended to improve coating properties by changing surface tension. A solvent mixture of solvents. When these solvents are exemplified, they are as follows. ο) An aprotic polar organic solvent (hereinafter, an aprotic polar organic solvent) which is a good solvent for poly-proline and soluble polyimine, and the second example can be exemplified by a group of methyl-2_pyrrolidone and two. Methyl imidazoline § the same, methyl hexylamine, methacrylamide, hydrazine, hydrazine-dimercaptoacetamide, bis-dimercaptopurine, bis-diethylcarbazone, and (tetra), I Ding _, γ • _. Among these, 例_^ pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, 丫-valerolactone, and the like are more preferably exemplified. The soil (2) is changed to the surface tension, the coating property, etc., and other solvents, for example, alkyl lactate, yam 3 ^ 101 200813158 24843 pif oxyheptanol, tetrahydronaphthalene, iso Ethylene glycol monoalkyl ether such as phorone or ethylene glycol monobutyl ether; diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether; ethylene glycol monoalkyl ether or phenyl acetate; a propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether or propylene glycol monobutyl ether; dipropylene glycol monoalkyl ether such as dialkyl malonate or dipropylene glycol monodecyl ether; These ester compounds such as acetates. Among these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monodecyl ether, and the like are more preferably exemplified. ^ 丄*τ ΙΛ 七,▼ r? -Η- /,L·,七七,τ r? > \ -rn r^> 刁P 'Beeting Ί生Ί王汾肖y Han Liu Bath/角里矢Behan, WJ gas y liquid crystal alignment agent printability, coating properties, solubility and storage stability, etc. are appropriately set. On the other hand, the solubility and storage stability of the aprotic polar solvent are superior to those of other solvents, and other solvents tend to be excellent in printability and coating properties. As described above, the liquid crystal alignment agent of the present invention may also contain various additives. As the various additives, a polymer compound other than polyamic acid or a derivative thereof or a low molecular compound can be selected and used depending on the purpose. For example, a polymer compound which is soluble in an organic solvent is used as an additive, and by adding these additives, electrical characteristics and alignment properties of the formed liquid crystal alignment film can be controlled. Examples of the polymer compound include polyamine, polyamino phthalate, polyurea, polyester, polyepoxide, polyester polyol, and polyoxygen modified polyamine. Formate, polyoxymethylene modified polyester, and the like. Further, as an additive of a low molecular compound, for example, (1) a surfactant may be used for a related purpose when it is desired to increase the coatability, (2) at 102 200813158 24843pif

When it is necessary to increase the antistatic property, the adhesion between A and the substrate and the abrasion resistance _ '3) can be used to increase the coupling agent, and (4) is low; wTi^ can be used as a ruthenium coupling agent and titanium ruthenium amide. In the case of the _ 4 醯 醯 舰 舰 舰 , , , , , 醯 醯 醯 醯 醯 醯 为 为 为 为 为 为 为 为 为 为 为 为 为 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合Alkyl group: a group of a minus wei, called an aminoethyl group) each aminopropyl methyl three: lactyl-wei, p-aminophenyl trimethoxy- Wei, _ phenyl phenyl triethyl lactyl (four), axis Silk-based methoxy-, meta-amine|phenyldiethoxy=alkane, 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxy hydrazine=, 3_glycidyloxy Propyltrimethoxy decane, 3-glycidoxypropyl decyl decyloxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethylsulfonium, 3-chloropropane曱 methoxy dimethoxy decane, 3- chloropropyl tridecyloxy decane, 3-mercapto propylene methoxy propyl trimethoxy decane, 3 fluorenyl propyl dimethoxy decane, N _ (l, 3-dimethylbutylene)-3-(triethoxyhydrazine

The alkyl group is 1-propylamine, the air enthalpy_bis[3_(trimethoxydecyl)propyl]ethylenediamine, and the like. As an example of the ruthenium amide catalyst, it is preferred to add an aliphatic amine such as trimethylamine, diethylamine, tripropylamine or tributylamine; N,n-didecylaniline, N,N-di Aromatic amines such as ethyl aniline, mercapto substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted porphyrin, hydroxy substituted quinoline, isoquinoline, methyl substitution A catalyst such as an isoquinoline, a trans-substituted isoquinoline, an imidazole, a mercapto-substituted imidazole, a hydroxy-substituted imidazole, or the like. In particular, N,N-dimercaptoaniline, o-103 200813158 24843pif, p-hydroxyaniline, o-, m-, p-hydroxypyridine, isoquinoline and the like. The addition amount of the Shi Xiwen coupling agent is usually 0 to 10% by weight, preferably 1 to 3 % by weight based on the total weight of the polyamic acid or the derivative thereof. The addition amount of the ife imidization catalyst is usually equal to 0 ^ 5 equal amount with respect to the 'base' of the poly-proline or its derivative, and is preferably 0. 05 to 3 equivalent. The amount of other additives added varies depending on the application, usually poly

The total weight of the tyrosine acid or its derivative is from 0 to 30% by weight, preferably from 0.1 to 10% by weight. Other preferred embodiments of the liquid crystal alignment agent used in the present invention are a combination of one or more polylysines. For example, in the case of a liquid crystal alignment agent containing two kinds of polyamic acid, a liquid crystal alignment agent containing a first polyamine and a second polyamic acid; and the tetraamine dianhydride and the second amine are used. A compound having a side bond structure in one or two of the amines, and a tetracarboxylic dianhydride and a compound having a side chain structure in any of the amines are not used in the second polyamic acid. More specifically, one or two of the A component and the β component of the poly-_' acid' are reacted with the A component of the amine to convert it to (iv) an amine acid or a derivative thereof (hereinafter, referred to as (tetra) aminic acid) The other is a poly-acid or a derivative thereof obtained by reacting two or two components of the acid component A and the component B with the amine component B (hereinafter, also referred to as "polyammonium citrate" "). A poly-acid of the invention! The composition with polyphosphonium amide is prepared by mixing the above-mentioned poly brittle 1 with poly-_. The weight ratio of the mixed polyamic acid 1 to the polystyrene citrate is preferably I / Π = 99 / 1 ~ 104 200813158 24843pif 50 / 50 'better is I / Π = 95/5~80 /20. The weight ratio can be appropriately adjusted according to the obtained pretilt angle, and if the ratio of the polystyrene is increased, the pretilt angle can be increased. Further, the liquid crystal alignment agent of the present invention may contain only a polyglycolic acid and a ruthenium, and may further comprise a polylactic acid derivative other than a polyacid. Lithium diamine I, using one or more diamines, at least

It is used for the diamine represented by the above formula (Π)~(Μ). The polyamic acid synthesized from the sulfonium component of the amine and the S carboxylic acid dianhydride can effectively impart a liquid crystal display element comprising a liquid crystal alignment film formed using the liquid crystal alignment agent containing the polyglycolic acid. Good ion density. Alternatively, any of the direct diamines may be used in combination as needed. Here, examples of the other diamine include the above-mentioned general formula (dummy) bis(涎), (diamine represented by hydrazine, or diamine of the residue, and diamine of the residual calcined diamine). The ratio of the aforementioned amine in the amine can be determined based on the selected structure of the diamine represented by the above formula (?) to (fox), and the desired ion density and long-term reliability. ^好是卜(10)%, more preferably 5~战. In another aspect, the above polyphosphonium phthalate can preferentially impart a liquid crystal alignment formed by a liquid crystal alignment agent containing cerium containing the polyaminic acid n. The crystal display element is at a suitable pretilt angle. / / The above-mentioned amine B in the diamine of the poly-proline D is used as a dry & knife represented by the formula (Μ)~(M) (1) one or more of the above-mentioned 105 200813158 24843pif diamines, but as the diamine which can be used in combination, a diamine or a fluorinated diamine represented by the above formula (I) to (W) may be mentioned. Wait. The combination of the polyamic acid I and the polyamic acid 2 (mixed δ) imparts a preferred property to the liquid crystal alignment agent of the present invention. Specifically, the diamine which is a raw material of polylysine can be imparted with a liquid crystal alignment by using the type and combination of the diamines which are used as appropriate. The film has a better ion density and a suitable pretilt angle.

<5. Liquid crystal alignment film of the present invention> / /, "The film" is a liquid crystal alignment in which the poly-acid and the modifier of the liquid crystal alignment agent of the present invention are simply calcined, and the liquid crystal is described. For the alignment film, for example, the liquid of the present invention can be applied to a substrate for measurement such as gasification of a liquid crystal display element. ° f, j ' is formed by heating the film of the liquid crystal alignment agent to, for example, 150 to 〜10 to 280 t. Here, the outer diameter of the liquid crystal alignment film is preferably 10 to 300 nm, more preferably 30 to 10 (10). In addition, the father is good, and the liquid crystal alignment film is polished. Liquid crystal: The film thickness of the crystal alignment film can be adjusted according to the viscosity and thickness of the liquid crystal alignment agent. Further, a well-known component such as a film thickness measuring device (ellipsGmetef) of the liquid crystal alignment film is measured. Further, according to f, the liquid crystal alignment film is subjected to a process such as a solution, and a general analysis such as 1 nMS can be used. 106 200813158 24843pif <6. Liquid crystal display element of the present invention> The liquid crystal display element of the present invention includes a substrate, (2) a pair of counter electrode substrates in which the pair of substrates are opposed to each other facing each other and (3) sandwiched between the ones of the present invention and formed in the opposite direction of the present invention (for example) glass substrate). The transparent substrate is a transparent substrate, and at least one or two of the substrates are provided on the surface of the liquid crystal display element, and the electrode formed on one surface of the root plate is not particularly limited. The base of the metal and the like. The X-V electrode, for example, the electrode: on the substrate, is placed on the surface of the substrate, and the electrode of the electrode on the substrate on which the electrode is disposed is aligned with the film. The formation of the liquid crystal alignment film of the present invention is carried out as described above. For the,,,,,,,,,,,,,,,,,,,,, This negative white (iv) positive liquid crystal composition and any composition of the liquid crystal composition having a dielectric anisotropy. Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent No. 2635435, Japanese Patent, Japanese Patent No. 2,635,435, Japanese Patent No. 2,635,435, Japanese Patent No. 2,635,435, Japanese Patent No. 2,635,435 Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei 9-241644 (ΕΡ 885 272 Α 1), Japanese Khan, No. 9-302346 (Ερ8〇6466Α1), Japanese Patent 107 200813158 24843pif _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Shili 4 Kaiping 1〇-204〇16 Bulletin (5) 844229 Sichuan, Japanese Patent t Kaikai 1〇1〇2436 Bulletin, Japanese Talent, Patent Special Kaiping 101-2 Difficult 2

Tim 4Lt",]#F" 2〇00'087040 ^ Open 2001 — 48822, etc.廿 贿 晶 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 显示 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 贿 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶Japanese Patent Special Kaiping 4 This special edition special Kaiping 8 - Na 3 bulletin, 曰 16807 ^ / ^ ~ 1〇 4869 bulletin, Japanese patent special Kaiping i0 - this patent, Japanese women's solution 1Q - delete 53 bulletin, Japanese Patent Deduction No. 10-236989, No. 236990, Japanese Special Edition (4) Kaiping 10_ This patent is open to the public, and is published in the Gazette of the Japanese Patent Special Publication No. 1〇〇〇-237〇〇〇 a = = 1ΰ— 2_ bulletin, Japanese patent special 2 237024 *5 tiger bulletin, Japanese too straight fortune | oy i〇^2t7〇7?; I! 10~237035 a fine 6th second daily newspaper, Japan special _ flat 〇 - (5)嶋U1), Japanese specialization-237 butterfly publication, this patent special (four) 1G__287875 1G 287874 #u bulletin, Japanese 287875旒 bulletin, Japanese patent special Kaiping 10_108 200813158 24843pif 291945, Japanese patent special Kaiping m patent patent u- __ bulletin, Japanese Patent Report, 曰2 face number bulletin, Japanese patent special opening 2〇〇 = ^; ^_- ==;: r726, added liquid display element Of course, also have other components. φ Erguang uses the color of the thin film transistor to display the TFT type visitor. There are thin film transistors, insulating two films and pixel electrodes:: black matrix, color filter, flattening element ^ outside ^ display component especially ms A liquid crystal display j* is formed on the substrate and has a micro-representation called a region (d_in). Further, the liquid crystal display element of the present invention may be formed by any method by forming the panel gap adjusting interval 2 between the substrates, for example, by the method of =1 column steps: (1) the two transparent transparent liquid crystal alignment agents In the step of (7) the step of applying the coated liquid crystal '(7) to the step of aligning the dried liquid crystal to 2 water, _ anti-counterfeiting, and reducing the film, (5) the red silk plate has a specific = mouth to paste After the step of 'liquid crystal sealing the substrate between the substrates, or 109 200813158 24843pif = liquid crystal drop is applied to the substrate and then bonded to another substrate for the step of aligning the liquid crystal alignment agent The coating method, such as a rotator method, a printing method, a jun, a master, a wood method, and the like. These methods can also be applied to the two-step method of the ink drop method 1 ink = the necessary infrared furnace in the infra-red furnace, and the method is known in the oven or the method. Heat treatment two inches. These methods may also be suitable for the present invention. Cognac (5"-i5〇~W^K^j'--Saki, preferably in the alignment of the CB== film to the film, in the iPS type liquid crystal display element, -, member element, TM type The liquid crystal display element and the sTM type liquid crystal are usually polished. In the VA type liquid crystal device, the polishing process is often not performed. The day and day are remarkable. Then, the adhesive is applied and adhered to one piece. The substrate may be formed by curing the adhesive used to form the liquid of the present invention, or a polarizing film may be attached to the liquid crystal display element of the present invention, a wavelength plate, a light-scattering film, a driving circuit, or the like. [Embodiment] 110 200813158 24843pif Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to these Examples. Further, the names of the tetracarboxylic dianhydride, the diamine, the alkenyl substituted nadic acid ruthenium imide compound, the heterocyclic compound and the solvent used in the examples are indicated by the following ellipsis. [tetracarboxylic dianhydride]

Pyromellitic dianhydride {structural formula (1) } : PMDA 1,2,3,4_cyclobutane tetracarboxylic dianhydride {structural formula (19) } : CBDA

[diamine]

- - - Amino group - a base of the base - [Structure (V - 1) } · DDM 4,4-[1,3_propane double (4, M phenylene methylene)] bis [aniline] {Structure formula (W-2) } : BABZP3 Phenylmethyldiaminobenzene {Structure formula (!γ_ 16)> :phPDA pentyl [UL biscyclohexyl]I group)phenyl]fluorenyl]diamine group Benzene {general (砸5) /R23 = c5Hn} : 5ChCh

1,1_bis[4_(4-aminophenyl)phenyl]_4_heptylcyclohexane "General formula (冱2 2) /R29=C7H15} : 7ChBZ

U-bis[4-(4-aminophenoxy)phenyl](trans_4_n-hexylcyclohexyl)3⁄4 hexane = General formula (XI-4) /R30 = C5Hn} ·· 5ChChBA 4, 4-vinyl-monoamine "Structure formula (v _7)": det [alkenyl-substituted nadic acid ylide imine compound] The compound represented by the following structural formula (lna-: βΑΝΙ_ [52] 111 200813158 24843pif

[Ethylene oxide compound] 4,4匕-indenyl bis(n,n-diglycidylaniline): DGA (3-glycidoxypropyl)trimethoxy decane: tms (3·& Glycidoxypropyl)methyldimethoxyoxydecane: DMS 2^(3, 'epoxycyclohexyl)ethyltrimethoxydecane: [oxetane compound] bis[(3- Ethyl I propylene oxide decyloxy) fluorenyl] stupid: BMMB [aziridine compound] 2,4,6_tris(1!-aziridine)-1,3,5-three Oxazine: ΑΤΑ [thiirane compound] N, N, N', N'-tetrathiopyranylmethyl 4,4,-diaminodiphenyl decane: TMAP ^ [^ ϋ ϋ ϋ 林Compound] Poly(styrene-co-2-isopropenyloxazoline) (manufactured by Nippon Shokubai Co., Ltd.: EPOCROS RPS - 1005) : PSO [oxazine compound] bis(3-propenyl-3,4- Dihydro-211-1,3-benzoquinone. Oxazine _6_yl) 曱 ((Four types of chemical industry stupid and noise azine type Fa): B0Z ") f^ (0 [solvent]

N-methyl 1 pyrrolidone: NMP butyl cellulolytic (ethylene glycol monobutyl _) : BC 112 200813158 24843pif <1· Synthesis of polyglycine> [Synthesis of polyaminic acid] Synthesis example 1 Add 1.6760 g of 5〇 to a 100 mL four-necked flask equipped with a thermometer, a scrambler, a raw material input port, and a nitrogen-conducting population! 〇1, 1.7918

PhPDA, and 3·3 g of dehydrated NMP were stirred and dissolved in a dry nitrogen stream. Then, 2.5321 g of CBDA was added and the mixture was allowed to stand at room temperature for 30 hours. In the case where the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 70 ° C or lower to carry out the reaction. To the resulting solution, 37.7 g of ® C 5 was formed into a 6% by weight poly-aracine solution (pa 1 ). The obtained PA1 had a weight average molecular weight of 37, 〇〇〇. Here, the diluted polyamine acid is diluted to a polyaracine concentration of about 1% by weight in a diluted night (phosphoric acid/dmf, 100 · weight ratio) composed of phosphoric acid and DMF, and Chromatopac c-R7A (Shimadzu) is used. In the second production, the above-mentioned diluent is used as a developing solvent, and the weight average molecular weight tH of the polylysine is determined by the GPC method, and the polystyrene acid is converted into a polystyrene. The column is made of GF-7HQ (Showa Denko) The conditions were measured under the conditions of a temperature of 50 ° C and a flow rate of 0.6 mL/min. Synthesis Examples 2 to 6 were synthesized in accordance with Synthesis Example 1 except that four tetrahydrous dianhydrides and diamines were changed as shown in Table 1. Polylysine solution (PA2 to PA6). The results including Synthesis Example 1 are collectively shown in Table i. [Table 1] Table 1 113 200813158 24843pif

<2. Preparation of liquid crystal display element> [Example 1] A polyglycine solution (ΡΑ1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a concentration of 6 wt% synthesized in Synthesis Example 2 were collected. The amine acid solution (ΡΑ2) was mixed at a weight ratio of 1/9. In the obtained mixture, 1 () part by weight per 1 part (8) parts by weight of the polythene surface is used as a DGA of the county-dick yttrium imide compound, and DGA as an epoxy W compound, and the improvement of these compounds is included. The total amount of the agent was adjusted to 2 〇 by weight ^ and then a mixed solvent of NMP/BC = 1/1 (weight ratio) was added. The liquid crystal alignment member was prepared using (4) at 4% by weight. The liquid crystal alignment agent of the liquid crystal display unit is produced by the following method. The cup is made of the following liquid crystal alignment agent, and the liquid crystal alignment agent is applied to two glass soils with 1 T electrode, forming a film thickness of 7 〇nm film. After coating the film at 80. The underarm was heated and dried 114 200813158 24843pif for about 5 minutes, followed by heat treatment at 220 ° C for 40 minutes, followed by grinding treatment to form a liquid crystal alignment film. The liquid crystal alignment film formed on the glass substrate is ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in an oven at i2 (rc): drying. The knife clock spreads 4 μηι on a piece of glass substrate. The spacer is formed such that the surface on which the liquid helium alignment film is formed is the inner side, and the polishing direction is parallel in the opposite direction, and the pair of glass substrates forming the liquid crystal alignment film are opposed to each other, and then the epoxy resin is used as the liquid crystal alignment film. The surrounding seal 7 is formed with an anti-parallel ceil having a spacing of 4. In this unit, the liquid crystal composition j shown below is injected into the space, and the liquid crystal composition is used as an injection port with a light hardener. After sealing, heat treatment was performed for 30 minutes at il 〇 ° C to produce a liquid crystal display element.

Liquid crystal composition I 115 200813158 24843pif

H F

5wt% 7wt%

Bwt% 8 wt% 14 wt% 14wi% 1Q wt% 10 wt% 12 wt% 12 wt% [Example 2] A concentration of 6 wt% of polylysine solution (PA1) synthesized in Synthesis Example 1 and a concentration 6 synthesized in Synthesis Example 3 The wt% polyamine solution 116 200813158 24843pif (PA3) was mixed at a weight ratio of 1/9. In the obtained mixture, 10 parts by weight of BANI-]VI as an alkenyl-substituted dysinoid compound, and B〇z as an oxazine compound are added per part by weight of the poly-proline, and the improvement of these compounds is included. The total amount of the agent was set to 2 parts by weight. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylactoic acid was diluted to 4% by weight based on the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

The 6% by weight polylysine solution (/?) synthesized in Synthesis Example 1 was mixed with the 6% by weight polylysine solution synthesized in Synthesis Example 3 at a weight ratio of 1/9. In the obtained mixture, 1Q parts by weight of each of the _ «acids as a substitute for the quinone imine compound ΒΑΝ — - M, and ~ compound BMMB, will be given to a few people (〇Xetane) 20 parts by weight . Subsequently, the total amount of the modifier of the Guangwu 5 is set to one, and then NMP/BC== 1/1 (weight m, Japanese 4«%, '1:; liquid helium alignment agent. A liquid crystal display element is produced by means of clothing. The same method as in the case of the application of the same [Example 4] (10) === coffee-amino acid solution (10)) in a weight ratio of two:: part by weight of poly-117 200813158 24843pif acid bismuth The bani^m, hydrazine of the imine compound will contain the modification of these compounds: and as the aziridine compound, NMP/BC=l/l (the total amount of the hydrazine is 20 parts by weight. A liquid crystal alignment agent was prepared by using the obtained liquid crystal alignment agent in a mixed solvent of 4 weight ratio with respect to the whole to prepare a liquid crystal alignment agent. Display component. ί Embodiment 1 produces liquid crystal in the same manner as in Example 1 [Example 5]

The concentration Θ (PA1 ) synthesized in Synthesis Example 1 and the weight % polylactoic acid solution synthesized in Synthesis Example 3 (PA3U: < weight ratio 1/9 were added to the present weight % of the polyamine acid solution solution weight In the _(4) sub-county addition compound, the ΒΑΝί\ part of each of the 100 bismuth imidate compounds is substituted as a dilute group, and the compound is included as a thiopyran compound. Subsequently, anmp/bc is added. The total amount of the =i/i agent is set to 2% by weight, and the polyglycolic acid is diluted to a mixed solvent with respect to the whole weight. Use the resulting liquid crystal alignment agent, :! Amount % to prepare a liquid crystal alignment liquid crystal display element. The same manner as in Example 1 was carried out in the same manner as in [Example 6], riding a synthetic example, a synthetic tannin & 壬曰 (and) and a synthetic polyglycolic acid solution (PA3) synthesized in Synthesis Example 3 by weight. Mixed than 1/9. The polyamic acid melt of the yttrium/niobium is added to the 1G and = surface, respectively, and the BANI-M-substituted Nadickic acid bismuth per _ weight of the imine compound will contain the modifier of these compounds. Total 118 200813158 24843pif A mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 7] A 5% by weight poly-proline solution (PA1) synthesized in Synthesis Example 1 and a 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3 were subjected to a weight ratio of 1/ 9 mix. In the obtained mixture, 30 parts by weight per 100 parts by weight of the 1'-concentrated sputum basket, and the BANI-Μ of the 1% Gonadic acid compound, and the weight of each 100 parts by weight 10 parts by weight of guanamine was added as a oxime compound, and the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the polyaminic acid was diluted to 4 parts by weight with respect to the whole. /〇 to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 1] A 6% by weight polyamic acid solution (PA1) synthesized in Synthesis Example 1 and a 6% by weight polylysine solution (PA2) synthesized in Synthesis Example 2 were subjected to a weight ratio of 1/1. 9 mix. To the resulting mixture, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight based on the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 2] A 6% by weight polylysine solution 119 200813158 24843pif (PAl) synthesized in Synthesis Example 1 was mixed with 6% by weight of poly(PA3) synthesized in the synthesis. In the mixed solvent of the obtained mixture = NMP / BC = 1 / 1 (weight ratio), polyglycine was 4% by weight based on the whole to prepare a liquid crystal alignment agent. Using the = crystal alignment agent as the liquid crystal display in the same manner as in Example i / [Comparative Example 3] T °

The polyhexanoic acid (ΡΑ1) having a concentration of 6% by weight synthesized in Synthesis Example 1 and the polyamic acid solution (ΡΑ3) having a concentration of 6% by weight synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the resulting mixture, 10 parts by weight of an alkenyl-substituted nadic acid yttrium compound was added per 1 〇〇 of the heavy poly-polyamine. Subsequently, a mixed solvent of aNMP/bc = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in the above, using the obtained liquid crystal alignment agent. [Comparative Example 4] A 6% by weight poly-proline solution (PA1) synthesized in Synthesis Example 1 and a 6 wt% poly-proline solution (PA3) synthesized in Synthesis Example 3 were subjected to a weight ratio of 1/1. 9 mix. To the resulting mixture, 10 parts by weight of ps() was added per gram of the polyglycolic acid. Subsequently, a mixed solvent of NMP/BC-1/1 (weight ratio) was added, and polylactoic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element 0 was produced in the same manner as in Example [ [Example 8] 120 200813158 24843pif In a concentration of 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3, 100 parts by weight of polylysine is added to 10 parts by weight of BANI as an alkenyl-substituted nadic acid ylidene compound and DGA as an oxirane compound, and the total amount of the modifier containing these compounds is added. Set to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight based on the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and the liquid crystal composition shown below was used. Liquid crystal composition

F

C〇H

17wt.°/〇

17wt%

C3h7

16wt% 121 200813158 24843pif

C2h4

F

F tOwt.%

F

5wt%

F 10wt%

6wt.% /\ ίΓ"\ f/\

6 wt·% 13 wt% [Example 9] In a 6% by weight poly-proline solution (PA2) synthesized in Synthesis Example 2, 10 parts by weight per 100 parts by weight of polyglycine was added as an alkenyl-substituted sodium. The BANI of the dick bismuth imidate compound and the oxime compound as a oxazine compound set the total amount of the modifier containing these compounds to 20 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained liquid crystal alignment agent and the liquid crystal composition were used. 122 200813158 24843pif [Comparative Example 5] In a 6% by weight poly-proline solution (PA3) synthesized in Synthesis Example 3, 20 parts by weight per 100 parts by weight of polymyric acid was added as an alkenyl-substituted naphthoic acid hydrazine. BANI of the imine compound - Μ. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained liquid crystal alignment agent and the liquid crystal composition were used. "salt >> 1 ΑΊ |[Bei aivej丄^" A 6% by weight polyphosphamic acid solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamine synthesized in Synthesis Example 5. The acid solution (PA5) was mixed at a weight ratio of 8/2. To the obtained mixture, 20 parts by weight of BANI-oxime which is an alkenyl-substituted nadic acid ruthenium imide compound per 100 parts by weight of polylysine, and 20 parts by weight per 100 parts by weight of polyglycine as epoxy B The TMS of the alkane compound, the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example Π] A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were used in a weight ratio of 8/ 2 to mix. In the resulting mixture, 20 parts by weight per 100 parts by weight of polyglycolic acid is added as an alkenyl-substituted naphthoic acid 醯 123 200813158 24843pif

BANI of the imine compound - Μ ' Further, 20 parts by weight of DMS as an oxirane compound was added per 100 parts by weight of the polyaminic acid, and the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4 wt% relative to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element T was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent.

[Example 12] A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were used in a weight ratio of 8/ 2 to mix. In the obtained mixture, 20 parts by weight of BANI as an alkenyl-substituted nadic acid-based imine compound is added per 1 part by weight of polyamic acid, and 20 parts by weight per 1 part by weight of polyglycine is added. As Ecs of an oxirane compound, the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment. [Example 13] A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight polyamic acid solution (PA6) synthesized in Synthesis Example 6 were used in a weight ratio of 8/ 2 to mix. In the resulting mixture, every IQ. 20 parts by weight of BANI-M as an alkenyl-substituted nadic acid-based imine compound, and 20 parts by weight of TMS as an oxirane compound per 100 parts by weight of polyglycine The total amount of the modifier containing 124 200813158 24843pif containing these compounds was set to 4 parts by weight. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 14] A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA6) synthesized in Synthesis Example 6 were used in a weight ratio of 8/ 2 mixed. To the obtained mixture, 20 parts by weight of BANI-oxime which is an alkenyl-substituted nadic acid ruthenium imide compound, and 20 parts by weight per 1 part by weight of polyglycine are added per 1 part by weight of polyglycine. As the ECS of an oxirane compound, the total amount of the modifier containing these compounds was 40 parts by weight. Subsequently, a mixed solvent of NMP/BC = l/i (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 6] A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were used at a weight ratio of 8 /2 mixed. To the resulting mixture, 20 parts by weight of U-containing amine Uu was used as an alkenyl group to replace the BANI-oxime of the nadic acid-based imine compound. Subsequently, a mixed solvent of gallium (five) and eight (by weight) was added to prepare a liquid crystal alignment agent by using polystyrene sulphate # j U ^ ^ 0 / , which was selected to be 4% by weight relative to the whole. A liquid crystal display element was produced in the same manner as in Example 1 except that the obtained crystal forming agent was obtained by using Mt ^ ^ / ϊ 1 m 1 obtained. 〃, 125 200813158 24843pif [Comparative Example 7] A 6 wt% polyproline solution (PA4) synthesized in Synthesis Example 4 and a 6 wt% polyproline solution (PA5) synthesized in Synthesis Example 5 were prepared. Mix at a weight ratio of 8/2. To the resulting mixture, 20 parts by weight of ECS as an oxirane compound was added per 100 parts by weight of the polyamic acid. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was used to dilute the poly-proline to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 8] A 6% by weight poly-proline solution (PA4) synthesized in Synthesis Example 4 and a 6% by weight poly-proline solution (PA5) synthesized in Synthesis Example 5 were used in a weight ratio of 8/ 2 to mix. Subsequently, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyamic acid was diluted to 4% by weight with respect to the whole to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. Γ <3. Evaluation of electrical characteristics> [Test Examples 1 to 22] The liquid crystal display elements produced in Examples 1 to 14 and Comparative Examples 1 to 8 were measured for ion density and long-term reliability in electrical properties as follows. Determination of sex. (1) Measurement of ion density Measurement of ion density was carried out using a liquid crystal physical property evaluation device 6254 manufactured by TOYO Technica. The measurement conditions were: Waveform··Triangle wave, frequency: 126 200813158 24843pif 0.01 Hz, voltage: ±10 V, and the measurement temperature was 60°C. The smaller the ion density value, the better the electrical characteristics. The results are shown in Table 2. (2-1) Measurement of retention characteristics of ion density [Test Examples 1 to 14] The ion density [pC] was determined for the liquid crystal display element produced, and the retention characteristics were evaluated. The test method for maintaining the characteristics was as follows: The liquid crystal display element was allowed to stand in an environment at a temperature of 60 ° C for 100 hours, and the extracted ion density [pC] was measured over the course of time. The smaller the decrease in ion density (for example, the increase rate is less than 1.5 times: the increase rate (times) = 1 (8) hours after the ion density / initial (〇 hour) ion density), the better the ion density retention characteristics, and the electrical characteristics The long-term reliability is better. The results are shown in Table 2. 127 200813158 24843pif [Table 2]

-~22] =' evaluate its retention characteristics. Test method to maintain the characteristics of the two methods ^ liquid crystal display section at temperature (10). The ion density μ of the taken out was measured by placing the drop in the environment of c. The retention characteristic of the degree of ion density = ion density of (hours) is shown in Table 3. The long-term reliability of the other electrical characteristics is better.结128 200813158 24843pif [Table 3] Table 3 Project sample elapsed time [hour] Increase rate [times] 0 50 100 Test Example 15 Example 10 11 36 44 4.0 Test Example 16 Example 1] 13 26 30 2.3 Test Example 17 Implementation Example 12 17 25 27 1.6 Test Example 18 Example 13 10 20 24 2.4 Test Example 19 Example 14 13 30 37 2.8 Test Example 20 Comparative Example 6 24 58 140 5.8 Test Example 21 Comparative Example 7 15 53 110 7.3 Test Example 22 Comparison Example 8 28 157 198 7.1 As shown in Table 2 and Table 3, when a liquid crystal display element in which a liquid crystal alignment film of the above-described modifier is mixed is used, a decrease in ion density retention characteristics is remarkably suppressed. As described above, the liquid crystal alignment agent containing the polyamic acid and the above-described improver of the present invention has a high ion density when the liquid crystal alignment film of the liquid crystal display element is formed, and the retention property can be remarkably suppressed. [Simple description of the diagram] None. [Main component symbol description] None 0 129

Claims (1)

200813158 24843pif X. Patent Application Range: 1. A liquid crystal alignment agent, which is a liquid crystal comprising a poly-proline or a derivative thereof, an alkenyl-substituted nadimide compound, and a heterocyclic compound. An alignment agent, characterized in that: the aforementioned heterocyclic compound has one or two selected from the group consisting of ethylene oxide, oxocyclobutane, thiopyran, azopropionate, 11 acetonin, and noise. The above heterocyclic structure. 2. The liquid crystal alignment agent according to claim 1, wherein the alkenyl-substituted nadic acid ylide compound is a compound represented by the following formula (Ina), [Chemical Formula 1] In the formula (I na), R and R2 each represent hydrogen, a carbon number of 1 to 12, a carbon number of 3 to 6, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or a benzyl group. η represents an integer of 1 to 2, and when η=1, R3 represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, and - (CqHsqhOt^CrH^rO^-CsH^s+i (q, r, S respectively represent integers of 2 to 6, t represents 0 or 1, U represents an integer from 1 to 30), and polyoxyalkylene alkylene represented by a group represented by -(R)V-C6H4-R4 (V represents 0 or 1, R represents a carbon number 130 200813158 24843pif 1-4 alkyl group, and R4 represents hydrogen or an alkyl group having 1 to 4 carbon atoms) a group represented by -C6H4-T-C6H5 (丁表*_ch2-, -C(CH3)2-, -CO-, _s- or -S〇2_), or a direct bond to the aromatic ring of these groups 1 to 3 hydrogens of the knot are substituted by a radical, when n = 2 'R3 represents a carbon number of 2 to 20, and a carbon number of 5 to 8 is extended to (CcftqOMCrHhOVCsHy (q, r) , s respectively represent an integer of 2 to 6, t represents 〇 or 丨, u represents an integer of 丨~3〇) Ο u is not a polyoxyalkylene group, carbon number 6~12 Aryl group, with gas R)V-C6H4-P?- (v represents 〇 or 2, R and r5 respectively represent carbon number, 4 alkyl group or carbon number 5~8 ring alkyl group) a base represented by -C6H4-T-C6H4- ( τ represents _CH2...-C(CH3)2_ ...c〇..., -OC6H4_C(CH3)2_C6H4〇·, _s_, or _), or One or the compound represented by the (four) ring straight seam knot, which is represented by the second paragraph of the shouting county, which replaces the Sakke_Asian compound-more than one, ina~3) [Chemical 2] 131 200813158 24843pif 4. The liquid crystal alignment agent according to claim 1, which comprises the above-mentioned alkene in an amount of from 1 to 100 parts by weight based on 100 parts by weight (based on the total amount) of the polyamic acid or derivative thereof Substituting a Nadick acid ylide imine compound. 5. The liquid crystal alignment agent according to claim 1, wherein the heterocyclic compound comprises a compound having two or more of the aforementioned heterocyclic structures, and comprises or comprises 100 parts by weight of the aforementioned polyamic acid or a derivative thereof. The substance (in total amount) is 1 to 100 parts by weight of the aforementioned compound. 6. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid or a derivative thereof reacts a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. The polylysine obtained. 7. The liquid crystal alignment agent according to claim 6, wherein the acid component comprises a cerium component and a cerium component, and the cerium component of the acid comprises an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic acid The anhydride is selected from the following 132 200813158 24843pif One or two or more compounds of the formulae (1), (2), (5) to (7) and (14), [Chemical 3] The liquid crystal alignment agent according to Item 7 of the present invention is characterized in that the aromatic tetracarboxylic dianhydride of the ash is a compound of the above structural formula (1). The liquid crystal alignment agent according to the seventh aspect of the invention, characterized in that the bismuth component of the bismuth acid comprises one or both of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride. . The liquid crystal alignment agent according to claim 9, wherein the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are selected from the following structural formula (19) One or two or more compounds of the group consisting of (23), (25), (35) to (37), (39), (44), and (49), [Chem. 4] 133 200813158 24843pif The liquid crystal alignment agent according to claim 10, wherein the alicyclic tetracarboxylic dianhydride is a compound of the above structural formula (19). 12. The liquid crystal alignment agent according to claim 6, wherein the amine component separately comprises an A component or a component comprising an A component and a cloud component, and the A component of the amine is selected from the group consisting of One or two or more compounds represented by the formula (I) to (W), [Chemical 5] 134 200813158 24843pif H2M_A1—mh2 In the general formula (I), A1 represents an integer of -(CH2)m·, and in the formula (dish), (¥), (fox), ^ independently represents a single bond, -〇_, -S -, Each S-, -S〇2_, _co"_c〇nh~nhc〇"c(cH3)2-, ^(=)2_, _2), _, _〇_(CH2)m_Q_, or _s_( cH2)m_s_, where m independently represents the Litong general formula (VI) of 1 to 12, and A2 independently checks -c(ch3)2_, ·_)2_ or carbon number two early = 〇_, -S -, -CO-, and the formula (Π)~(yu) $ stretching, hydrogen, may also be independently substituted into a cyclohexane ring of i τ or a 苯 3 Η 2 1 group of a benzene ring bond or The liquid crystal alignment agent according to claim 12, wherein the A component of the amine is selected from the following structural formula (IV). One of the groups consisting of -1), (rv-2), (rv-15), (iv-16), (vl)~(V-12), (V-33), and (W-2) Two or more compounds, [Chem. 6] Gate 2"Flying in η门2 (!V-1) 136 200813158 24843pif (V-1) h2n (V-3) H2N mh2 (\A10) (V-11) H2N 〇M2} HO OH H2N {V-33} The liquid crystal alignment agent according to claim 12, wherein the component B of the amine is one selected from the group consisting of the following general formulas (Μ) to (μ). Or a compound represented by two or more formulas, [Chem. 7] 137 200813158 24843pif In the general formula (M), R1 represents a single bond, -0-, -C0-, -C〇0-, -0C0-, CONH ... CH20-, -CF20_ or _(CH2)e-, and e represents 1~ An integer of 6 and R2 represents a group having a steroid skeleton, a group represented by the following formula (xm), an alkyl group having 1 to 30 carbon atoms, or a phenyl group, and the carbon number of the alkylene group and the alkyl group is When 2 or more, any of -CH2- may be independently substituted by 138 200813158 24843pif _〇-, -ch=CH- or -- (wherein the oxygen may not be independently fluorine, methyl, or oxime\ , 贝, 刖 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 R R R R R R R R R ! ~3 () of the base, R5 independent =, R4 represents hydrogen CH2-, also indicates no early bond, _CO- or Γ In the general formula (X), R3 independently surface or carbon from 1 to 3G, R5 alone; ^, R4 represents 氲-- R6 and R7 are independently, respectively; T; (10) or phenyl, ^ & 1 1 to 30 、, in the formula (XI), R represents hydrogen or carbon number 1 Any of the above-mentioned calcining bases of 2 to 2 may be independently substituted by the di-carbon 'carbon or · flavour (the towel Oxygen peach), the surface crucible or the carbon number 1 to 6 exfoliation group, ring A Represents ^-extended benzene T _ ring-extension hexyl group, a represents 〇 or 丄, b represents ^ 〇 or 丨, ^2, c independently represents the general formula (welcome) in 'R10 represents carbon number 3~3〇的烧美3 ~30, fluoride wire, R11 represents hydrogen, carbon number i ~ ^ ^ stone number of carbon number 1 ~ 30 - fluorinated fluorenyl group, Rl2 independently represents or two = ~ 6 alkyl, d Independently indicates 〇 or }, fire number 1 [化8] k _ 139 200813158 24843pif In the general formula (xm), ru, r is 4, and each of them is independently expressed as mouth = mouth, seven... C00-, -0C0-, -C0NH "Carbon number 4 is extended and the carbon number is 1 to 3 An alkyl group (wherein the oxygen is discontinuous), or a carbon number 7 alkyl group (wherein the oxygen is discontinuous), R 6 and RH each independently represent hydrogen, fluorine or fluorenyl, and R 18 represents hydrogen, fluorine or chlorine. , cyano group, alkyl group having 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkoxyoxyl group having 2 to 30 carbon atoms, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monofluoro group a methoxy group, a dimethoxy group or a trifluoromethoxy group, and the -CHy of any of the alkyl group having a carbon number of 2 or more and the alkoxyalkyl group may be difluoro The group is substituted by a group represented by the following formula (XIV), and the ring b and the steric respectively represent 丨, 'phenyl or 1,4-cyclohexyl, respectively, and f and g ^ each independently represent 0 to 4; The integers, i, j, and k respectively represent integers of 〇~3, and the total of these values is 1 or more, and 1 and m respectively represent 1 wei 2 '[9] (XIV) In the formula (xw), R19, R20, R21 and R22 each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and η represents an integer of 1 to 1 Å. The liquid crystal alignment agent according to claim 14, wherein the β component of the amine is selected from the group consisting of the following formula: 140 200813158 24843pif (Vffl: 4), (vin - 5), ( Shan—6), (χι_2), and (冱一4) a compound represented by one or two or more formulas of the group, [Chem. 10] )' // \=/ H2n (Vlli-S) In the above formula, R23 independently represents an alkane having a carbon number of 3 to 3 Å or an alkoxy group having a carbon number of 3 to 30, and r29 represents hydrogen or an alkyl group having a carbon number of 丨~3〇, and R represents hydrogen or a carbon number of 1. ~2〇的烧基. The liquid helium alignment agent according to any one of claims 1 to 15, which is characterized in that it contains two or more kinds of the above polylysine or a derivative thereof. 17. A liquid crystal alignment agent, wherein the liquid crystal alignment agent is a liquid crystal alignment agent comprising polylysine or a derivative thereof, a dilute-substituted nadic acid ruthenium imine compound, and a heterocyclic 141 200813158 24843pif compound, wherein the aforementioned Polylysine or a derivative thereof is a polyamic acid obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component, and the acid component contains an A component and a B component, and an acid component A Is a compound selected from one or more of the group consisting of the following structural formulae (1), (2), (5) to (7), and (14), and the B component of the acid is selected from the following structure Equations (19), (23), (25), (35) to (37), (39), (44), and (49) one or more compounds of the group consisting of the group, wherein the amine component separately contains the component A or two components of the component A and the component B, and the component A of the amine is selected from the following structure. Ethnic groups consisting of (IV-1), (iv-2), (rv-15), (IV-16), (v-1)~(v_12), (V-j3), and (grabbing-2) One or more of the compounds 'the B component of the aforementioned amine is selected from the following formulas (Μ-2), (M~4), (Shanyi 5), (Ship-1), (Edge 1) And a group consisting of (1), one or two or more compounds represented by the formula, and an alkenyl group substituted with a nadic acid ylide compound, comprising the following formula (Ina 1)~( The one or more of the compounds represented by ina-3) may be selected from the group consisting of epoxy epoxide, oxycyclobutane, and milano[nitrogen (tetra). The surface of the evil side, and the red scale of the group of Qin, or one or two of the heterocyclic structures from above, 〆 [Chem. 11] 142 200813158 24843pif (19) No 3) (25) (35) [Chem. 13] 143 200813158 24843pif (V,7) fV-8) (V-9) H2N (V-10) NH2 (V-41) (V^12) HO OH H2N (V«33) {Vii-2) [Chem. 14] 144 200813158 24843pif (阙(XM) In the above formula, R23 independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, and R29 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and represents hydrogen or carbon. Alkyl groups of 1 to 20, [Chem. 15] 145 200813158 24843pif The liquid crystal alignment agent according to claim 17, wherein the component A of the acid is a compound represented by the above structural formula (1), and the component B of the acid is In the compound represented by the above structural formula (19), the A component of the above amine is one represented by the above structural formulae (IV-16), (V-1), (V-7) and (W-2). Two or more compounds, the B component of the above amine is one or two or more compounds represented by the above formulas (M-5), (XI-2) and (XI-4), and the aforementioned alkenyl substituted Nadick The acid quinone imine compound is a compound represented by the above structural formula (Ina-1), and the aforementioned heterocyclic compound contains 4,4'-methylenebis(N,N-diglycidylaniline), (3- Glycidoxypropyl)trimethoxydecane, (3-glycidyl 146 200813158 24843pif oleylpropyl)methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, bis[(3-ethyl)-oxopropionylmethoxy)methyl]benzene, 2,4,6-bis(1'-azapropionyl)-1,3,5--Qin ^ ^'^^', ^4 mercaptomethyl-4,4'-diaminodiphenyl, alkane, poly(styrene-cod-isopropyl oxazoline), and bis(3-benzene One or more compounds of the group consisting of methane-3,4-dioxa-2Η], 3β"clumoxazinyl)methane. 19· A liquid crystal alignment film, characterized in that it will be as claimed The liquid crystal alignment agent according to any one of the items 1 to 3 is formed by calcining in a state of a film. 20--the liquid crystal display element ^ /, 疋 has a pair of opposite alignments = one or two of the opposing faces of the pair of substrates are formed on the film, and between the pair of substrates The liquid crystal component formed on the surface of the oxygen is characterized by the liquid crystal alignment film according to the liquid crystal display element of the liquid crystal layer formed by the liquid crystal.曰曰 曰曰 骐 is like the scope of patent application 19 147 200813158 24843pif VII. Designation of Representative Representatives (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: jfe 〇