TW200815878A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

The purpose of this present invention is providing a liquid crystal aligning agent for a liquid crystal display to improve a voltage retention rate and long-term reliability. The liquid crystal aligning agent of the present invention is a constitution comprising an alkenyl-substituted nadimide compound and polymer composition chosen from poly(amic acid) and derivatives thereof. The polymer composition is at least one polymers obtained from the reaction between tetracarboxylic dianhydride and diamine. The tetracarboxylic dianhydride is at least one of compounds represented by formulae (1)-(17).

Description

200815878 25623pif IX. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a nadimide having an alkenyl group substituted by an alkenyl group (the chemical formula is Endo-5-no; rbomene-2, 3-dicarboximide) a compound and a liquid crystal alignment agent of at least one selected from the group consisting of polyphosphoric acid and a derivative of the polyamic acid, a liquid crystal alignment film formed by the liquid crystal alignment agent, and having the liquid crystal alignment film Liquid crystal display element. [Prior Art] The liquid crystal display element is used in a viewfinder of a notebook computer or a desktop computer (deskt〇pc〇mputer) as a viewfinder for a video camera (camera). Among various liquid crystal display devices such as (viewfinder) and projection display, they have recently been used for televisions. Further, it can also be used as an optoelectronic (opt'oelectronic) related element such as an optical print head, an optical F〇urier transform element, or a light valve. The liquid crystal display device usually includes: 1) a pair of substrates disposed oppositely, 2) electrodes formed on one or both of the surfaces facing the pair of substrates, and 3) opposing pairs of the pair of substrates A liquid crystal alignment film formed on the surface, and 4) a liquid crystal layer formed between the pair of substrates. 7 200815878 25623pif The previous liquid crystal display element, which is mainly a display element using a nematic liquid crystal, twists a twisted nematic (TN) type liquid crystal display element of 9 degrees, and is usually twisted.

Super Twisted Nematic (Senior Twisted Nematic, STisQ type liquid Japanese wire member, use; 4 film transistor (transist〇r) so-called Thin Film Transistor (TFT) type liquid crystal Display elements and the like are being put to practical use. These liquid crystal display elements have the disadvantage that the angle of view of the image can be normally visually narrowed, and when viewed from an oblique direction, luminance or contrast reduction and halftone brightness inversion are generated. The problem of the above viewing angle is being improved by the technique of the following liquid crystal display element: a TN_TFT type liquid crystal display element using an optical compensation film, and a vertical alignment (VA) type liquid crystal display using a vertical alignment and an optical compensation film. Multi-domain vertical alignment (MVA) type liquid crystal display element using a vertical alignment and protrusion structure technique, and an in-plane switching (IPS) type liquid crystal display element of a lateral electric field type, 琶Electrostatically Controlled Birefringence (ECB) type liquid positive head component, optical compensation bending compe Nsated

Bend or Optically self_Compensated Birefringence: OCB) type liquid crystal display elements, etc., and improved techniques are being put into practical use or research. The technical development of the liquid crystal display element is realized not only by improving the above-described driving method or element structure but also by using the constituent members used in the liquid crystal display element. Among the constituent members used in the liquid crystal display element, in particular, a liquid crystal alignment film, which is one of the important elements related to the display quality of the liquid crystal display element, is increasingly important as the function of the liquid crystal display element. Day-to-day alignment film The liquid crystal alignment film can be prepared from the right θ • by / night 配 day alignment agent. At present, the main liquid helium-targeting agent is a solution obtained by making polyacrylic acid or a solvable solvent. This solution is formed into a film by heating or the like to form a polymer: amine film. The 曰 曰 ^ θ θ alignment agent with various polymers other than lysine is also studied, but it is heat-resistant and chemical-resistant.

UtaB, main fabric, liquid crystal alignment, electrical characteristics, optical characteristics, display characteristics, and the like are hardly practical. It is preferable that the display quality of the crystal display element is as shown in the liquid crystal alignment film. If the voltage holding ratio is low, the voltage applied to the liquid crystal in the frame time will decrease, and as a result, there is a case where the degree of freedom is lowered and the normal gray scale display is broken, so that the initial voltage holding ratio is high, and There is a case where the ritual retention rate (long-term reliability) is lowered after the high-temperature acceleration. In order to try to solve the above problems, several methods have been proposed recently. 1) A polylysine composition for forming a liquid crystal alignment film and combining two or more kinds of polyamic acid having different physical properties (for example, refer to Japanese Patent No. 19334S) Bull. No. 11-193347). + ^ inch open 2) A varnish composition containing a polymer component containing poly-_P〇lyamide and a solvent is known (for example, 参月?, International Publication WO 00/61684) . 9 200815878 25623pif 3) A varnish composition containing two or more kinds of polyamic acids and polyamines having different physical properties, and a solvent is known (for example, refer to International Publication WO 01/000733). 4) A varnish composition containing a polymer material containing a polyamine acid or the like synthesized using a diamine compound having a specific structure is known (for example, refer to Japanese Patent Laid-Open No. 2〇〇2-16263〇 Bulletin). • A technique of adding a low molecular weight oxy-resin to a polyimide and a polyamido varnish is known (for example, refer to Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. 6) In addition, the invention similar to the present invention is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-269491 and Japanese Patent Application Laid-Open No. Hei. However, the problems of voltage holding ratio and long-term reliability are not sufficiently solved by these prior art techniques. SUMMARY OF THE INVENTION In view of the above circumstances, it is desired to develop a liquid crystal alignment agent, a liquid crystal alignment agent for a display element, and a liquid crystal alignment agent using the liquid crystal alignment agent for a liquid crystal display element. A film, and a liquid crystal display element having such a liquid crystal alignment film in summer. ^才: Hair, people, etc., who are actively researching to solve the above problems, now use a liquid crystal alignment agent containing an alkenyl-substituted nadic acid hydrazide imidized human and poly-stannic acid or a derivative thereof. In order to form the liquid crystal alignment 2, the liquid crystal display element having the liquid crystal display element 保持' retention rate and long-term dependency can be imparted, thereby completing the present invention. Further, it is found that by appropriately selecting the above polylysine, a liquid crystal alignment film which can be suitably applied to liquid crystal display elements of various display driving methods can be obtained. The liquid crystal alignment agent of the present invention is represented by the following item [1]. a .................. [i] a liquid crystal alignment agent which contains an alkenyl substituted nadic acid, an imine compound, a self-polymeric acid and a polyt composition selected from the group consisting of polyamine derivatives and a solvent component, the polymer component being at least one of a polymer obtained by reacting four acid dianhydrides with a diamine, the tetracarboxylic acid Erxuan is at least one of the compounds represented by the formula (1) to the formula (17), and the ratio of the polymer component based on the total amount of the group = 0.5% to j Wt^ (% by weight), and the above The ratio of the alkenyl substituted nadic acid amine 2 compound is based on the weight ratio of the polymer component

200815878 25623pif

Wherein Ph represents phenyl (phenyl) and Me represents thiol (methyl). According to the present invention, it is possible to provide a liquid crystal display element of various driving methods having a high voltage holding ratio and long-term reliability 12 200815878 25623pif. The above and other objects, features and advantages of the present invention will become more apparent from the description of the preferred embodiments. "Arbitrary" means not only freely selectable, but also free to choose the number. Also, "arbitrary Λ can be replaced by B, c " ^ 」", which means that in addition to any A replaced by B

2. In the case where any A is replaced by C and any a is replaced by D, a case where a plurality of As are substituted by at least two of B to D is also included. For example, in any -CHr may be represented by an alkyl group, an alkenyl group, an alkoxy group (a tetrakis), an oxyalkyl group, an alkoxy group, Further, in the present invention, it is preferred that the two linked -CH2- are substituted by 〇- X. The compound represented by the formula (1) is sometimes simply referred to as a compound (1). The compounds shown by other t are also the same. In the chemical structural formula / in the present specification, when the substituent or the ligand is bonded to the ring, the bonding position can be freely selected. τ With respect to the side chain type diamine and the non-side chain type diamine, the definition of these terms is first explained in the related description of the one amine used in the present invention. The present invention is composed of the above [1] and the following [2] [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ a derivative of a polymer component of a derivative selected from the group consisting of 13 200815878 25623pif tetraacid dianhydride and a diamine The tetracarboxylic acid is a compound of the formula (16) and at least one of the compounds of the formula (17) or a compound of the formula (16) and a compound of the formula (17). At least one mixture of at least one of the compounds represented by the formula (1) to the formula (1)). [3] The liquid crystal alignment agent according to [1] or [2], wherein the nadic acid ylide compound substituted by the dilute group is a compound represented by the formula (a).

η (8) wherein R1 and R2 are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or a node 1, and η is 1 or 2, ^ η1, IT is an alkyl group having a carbon number of 丨~;^, a cycloalkyl group having a carbon number of 〜8, and an aryl group having an carbon number of 6 to 12 (anal) - BenZyl, -LL (〇V(L2〇)r_R4 (L) and l2 are independently alkylene having 2:6 carbon atoms, and R4 is an alkyl group having 2 to 6 carbon atoms. Is 亚 or 1 'and r is an integer from 1 to 30), _(l3)s_b2_r5 is a sub-alkyl group having a number of 1 to 4, s is 〇 or B2 is a phenylene group in which any chlorine can be substituted by VII ( Phenylene), and r5 is money as a base, or -BTB (B is an Ami in which any hydrogen can be replaced by _〇Ή, τ is -ch2-, -c(ch3)2-, -co-, -〇 _, _8_ or _8〇2_, and ^ 14 200815878 25623pif is any phenyl group which can be substituted by _0H), η is 2 4, and r is a sub-alkyl group, a dish, a ring having a carbon number of 2 to 2 Å. A stilbene 2 group, an arylene group having a carbon number of 6 to 12 (di 1), : (〇V (L QVL4_ (L), L2, and L4 are independently an alkylene group having a carbon number of 2 to 6, and q is a fluorene. Or 1, and Γ An integer of 1 to 30), _(l3)s_b2_l5_ (2L, tL5 is independently a sub-alkyl group having a number of breaks of 1 to 4, and 3 is: or i, a phenylene group in which any hydrogen can be replaced by _〇H) , _b2_丁七^ (B2 is independently a phenylene group in which any hydrogen can be replaced by -ΟΗ, and τ is 1 qing 2_, -co_, -〇-, -s- or _s〇2/) / or -B 〇 -B2_C(CH3) icy yttrium y y y y y y y y y y y y y y y y y y y y y y y y y y It is at least one of the formula (a-D~ formula (a~3). No. a 15 200815878 25623pif

(a-1) 〇

〇

(a-2)

The liquid crystal alignment agent according to any one of [1] to [4] wherein the diamine is a non-side chain type diamine selected from the group consisting of formula (I) to formula (VD). At least one of the ethnic groups, 16 200815878 25623pif

Nh2

H2N

H2n

(I) (II) (III) (IV) (V) (VI) (VII) nh2 wherein A] is a linear alkylene group having a carbon number of 2 to 12; and A2 is a straight carbon having a carbon number of 1 to 12 Chain alkylene; A3 is independently a single bond, _〇-, _CO-, -CONH-, -NHCO ... C(CH3)2-, -C(CF3)2_, -0-A2-0 ... S-, - SS-, -S02_, -SA-S-, or a direct bond sub-hospital based on a carbon number of 1 to 12, any of the hydrogens of the burnt sample and the benzene ring may be fluorine, 〇ί·3, -OH, - COOH, -S〇3H, Ρ03Η2, benzyl or hydroxybenzyl substituted. [6] The liquid crystal alignment agent according to any one of [1] to [4] wherein the diamine is selected from the group consisting of Formula (IV-1), Formula (IV-2), Formula (IV-15), and (IV-16), at least one of the group of the non-side chain type diamines represented by the formula (V-1) to the formula (V-13), and the formula (YH-2), 17 200815878 25623pif

(IV-1)

(,v~2) (IV-15) (IV-16) Η2Ν_^Ί〇γΝΗ2 Η2Νί〇Π〇γΝΗ2 (V_1) (V-2) (V-3)

f

(V-7)

The liquid crystal alignment agent according to any one of [1] to [4] wherein the diamine is a non-side chain type selected from the group consisting of formula (I) to formula (view). a mixture of at least one of a group of amines and at least one of a side-bonded diamine having a side bond group. 200820088878 25623pif The side bond group is an alkyl group having a carbon number of 3 or more and a carbon number of 3 or more. Alkoxy group, alkoxyalkyl group having a carbon number of 3 or more, a group having a steroid skeleton, and an alkoxy group having a carbon number of 3 or more at the terminal and an alkoxy group having 3 or more carbon atoms a group selected from the group of alkoxyalkyl groups of 3 or more, h2n~a1~nh2 (I)

A (II)

Wherein 'A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and A3 is independently a single bond, -〇, _c〇_, -C0NH_, 视( ^0 ... C(CH3)2~c(CF3)r, _〇_A2_〇_, each, each s_, H, or a linear sub-alkyl group having a carbon number of 1 to 12; Any hydrogen of the benzene ring may be substituted by fluorine, even, _〇H, _c_, and (d). The liquid crystal alignment agent according to [7], wherein the side chain type two press is selected 19 200815878 25623pif a diamine in the group of compounds of the formula (Μ)~(XU),

(wherein R6 is a single bond, _〇-, -CO-, -COO-, -OCO, -C〇NH-, -CH20-, -CF20-, or an alkylene group having 1 to 6 carbon atoms, Any -CHb- in the alkylene group may be substituted by _0-, -CH=CH- or -C-C-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a carbon number of a phenyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms as a substituent or a group represented by the formula (D-1), and any -CH2- of the alkyl group may be 0- , -CH=CH_ or -C three C-substitution,

Wherein R, 8, R19 and R20 are independently a single bond, -〇-, _COO-, -〇CO-, a CONH-, a sub-alkyl group having a carbon number of 1 to 4, and an oxygen having a carbon number of 1 to 3 An alkylene group or an alkyleneoxy group having a carbon number of 1 to 3; a ring B and a ring C are independently a 1,4-phenylene group or a 1,4-cyclodohexylene group; R21 and R22 is independently a fluorine or a fluorenyl group, and ml and m2 are independently 0, 1 or 2; e, f and g are independently an integer of 0 to 3, and the total of e, f and g is greater than or equal to 1; R23 is a carbon number of 3~ An alkyl group of 30, an alkoxy group having a carbon number of 3 to 30, or an alkoxyalkyl group having a carbon number of 3 to 30, and any of the alkyl group, the alkoxy group 20 200815878 25623 pif group and the alkoxyalkyl group. The hydrazine may be substituted by fluorine, and any of them may be substituted by a difluoromethylene or a group represented by the formula (D-2), R24 I Si-R26-〇-Si-R25 R27 7n (D-2) , R, IT, R26, and R2? are independent of the armored + Gan* Na I number of 1 to 10 or the base, and η is an integer of 1 to 1 ))

(IX) dR8 is independently chlorine or methyl: R9 is gas, _C0- or -CH ^

(X) 1〇-°-rio<^ R12 (〆, 中,R8 is independently hydrogen or sulfhydryl; R9 mountain 炫, or; ^% ... oxygen, rabbit number i 'read as 2~30 Base; R, stand alone =, 1^〇21 200815878 25623pif or -CH2-; and burnt base, or phenyl) R and R] 2 are independently hydrogen, carbon number

(XI) (wherein R13 is a dumpling ru ^ ^ ^ having a carbon number of 3 to 3 别, and any -ch2 of the alkyl group may be substituted by -a, _CH=CH_ or C5C_; ] 4 is an alkylene group having an independent carbon number of 1 to fluorene; ring A is 』4 f , s group 'a is 〇d'b is 〇, u2; and c is independently H2N\/=\ / /=v \ R15

C, wherein the number of ash is ～30, the alkyl group or carbon number is 1, and the alkyl group is alkyl; Rl6 is hydrogen, the alkyl group having a carbon number of 1 to 30 or the carbon number 〜" The carbon number is Pak and ·, d is independent of 0 or 丨). The alkylene (XII) amine is a liquid crystal alignment agent selected from the group consisting of (5) - 2), (5) - 5) and Diamines in the group of compounds, 22 200815878 25623pif

H2n

Selected from the formula (IV - U, ^ 4, wherein the non-side chain type diamine is a group of the formula (V-丨)~j(IV-2), the formula (^5), the formula (xv-16), the species / v_13) and the combination of formula (w-2)

—4) The group-type diamine is a group selected from the group consisting of a compound of the formula (M-2), a diamine of the formula (M, and a compound represented by the formula (5)-6). 23 200815878 25623pif

H2N

Nh2 (V-1)

(V-2)

(V-3)

(V-7)

NH〇 (V-10)

NH〇 NH2

(V-12) NH〇 (V-13)

(VII-2) 24 200815878 25623pif

(VIH-5) (VIII-6) wherein R28 and R29 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. [11] The liquid crystal alignment agent according to [1], wherein the polymer component is at least two selected from the group consisting of at least one of the compounds represented by the formulae (1) to (17). The polyamic acid or derivative thereof obtained by reacting at least one selected from the group consisting of the non-side chain type diamines represented by formula (I) to formula (W), by the above four Polylysine or a derivative thereof obtained by reacting at least one of tetracarboxylic dianhydride with at least one selected from the group consisting of a side chain type diamine represented by formula (M) to formula (XU), and 'Polyamic acid or a derivative thereof obtained by reacting the above tetracarboxylic dianhydride with a mixture of the above-mentioned non-side chain type diamine and side chain type diamine, 25 200815878 25623pif

26 200815878 25623pif

(wherein Ph represents phenyl, Me represents fluorenyl; polymer component is a mixture of at least two polymers) H2N - A1 - NH2 (I)

(wherein A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and A3 is independently a single bond, -0-, -〇3-, -CONH -, -NHCO-, -C(CH3)2-, -C(CF3)2-, -OA2-0-, -SS-, -S〇2_, -SA-S-, or a carbon number of 1~ The direct bond of 12, the cyclohexane ring and any hydrogen of the benzene ring may be replaced by fluorine, -CH3, -OH, 27 200815878 25623pif -COOH, -S03H, P03H2, benzyl or hydroxybenzyl) R7 I R6

(wherein R6 is a single bond, -〇, -CO-, -coo-, -CONH-, -CH2O-, -CF2O-, or a mercapto group having a carbon number of 1 to 6, and any of the alkylene groups -CH2· may be -〇-, -CH=CH- or substituted. R is a group having a steroid skeleton, a calcined carbon number of 3 to 30, an alkyl group having a carbon number of 3 to 30 or a carbon number a phenyl group having 3 to 30 alkoxy groups as a substituent or a group represented by the formula (D-1), and any _ in the alkyl group may be substituted by -〇-, _CH=CH- or -OC_ ,

Wherein, 18, R19 and R20 are independently a single bond, _〇_, _c〇〇_, -OCO-, -CONH-, an alkylene group having a carbon number of 1 to 4, and an oxygen atom having a carbon number of 〜3. An alkyl group, or an alkyleneoxy group having a carbon number of 1 to 3; a ring b and a ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R21 and r22 are independently a fluorine or a methyl group. m 1 and m 2 are independently 〇, 1 or 2; e, f and g are independently an integer of 〇 〜 3, and the total of e, f and g is greater than or equal to 1; R 23 is an alkyl group having 3 to 30 carbon atoms; Is an alkoxy group of 3 to 30 or an alkoxyalkyl group having a carbon number of 3 to 30, and among these alkyl groups, alkoxy groups and alkoxyalkyl groups, any hydrogen may be substituted by fluorine, and any _CH2 - may be substituted by a group represented by difluoromethylene 28 200815878 25623pif or formula (D-2), R24 / R26 - + Ή + - R25 · R27 4 (0^2) wherein R24, R25, R26 and R27 Independently a carboniferous alkyl or phenyl group, and η is an integer from 1 to 100) 〜, 1~1〇 of ί Ρ8 R9

(IX) (wherein R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group of a rock, or an alkenyl group having a carbon number of 2 to 3 Å; and, = 1 to 30 -CO- or _CHr) independently For a single button,

R11<)-〇-R10-^NH: R12 (X) (wherein R8 is independently hydrogen or methyl; R9 is hydrogen, an alkyl group of hydrazine, or an alkenyl group having a carbon number of 2 to 30; R10 is independently a mask Gold, ~30 n R and R independent of 虱, carbon number is alkyl, or phenyl) 30 of 29 (XI) 200815878 25623pif

-^NH; Wei is 3~% of the record, any *, (3) one CH- or 〇c_ replaced by this wealth; R14 is independently the carbon number of 1~ό by its ·, ^ ^ soil, Chen Hao 1,4-phenylene or cyclohexylene is or •... R1^

(XII) (A, R13 is an alkyl group having a carbon number of 3 to 3 Å or a disk number of 3 fluorinated m-hydrogen, Weiweibu 3 (): 30 of the mouse thiol group; R] 7 independent For the number of ~6, and d is independent of 〇 or 丨). The liquid crystal alignment agent according to the item [1], wherein the polymer component is at least two selected from the following 4 & _ 、, Π7Λ..〆田禋猎由式(π And at least one of the compounds shown in the formula (7)) and at least one of the compounds of the formula (17) and the servants of the formula (17) from aa \ τ γ m , one kilogram, and 1:7 From the formula (~f (the compound of the county is less than four kinds of mixtures - the anhydride is known from the formula (IV-υ, formula (Γν-2), formula (10)-15 αν-(6), formula (ν- υ~Formula (v-13) and formula (observation), a polyamine-oxime or a tau organism obtained by a kind of reaction, hunting by the above tetracarboxylic acid dianhydride and formula (M-4), formula (ship one) 5) and a poly (amic acid) or a derivative thereof obtained by reacting at least one kind of reaction of the side chain type 30 200815878 25623pif-amine represented by Han 忒~6) A polyamic acid or a derivative thereof obtained by reacting the above tetracarboxylic dianhydride with a mixture of the above-mentioned non-side chain type diamine and a side chain type diamine, η2ν~〇~ΝΗ2 Η2Ν^Γ' (IV-1) ( !V-2)

NH2

H2N-\\ "|^j--NH2 H2N

(V-3) (V-2)

(V-7)

NH2

(VI!-2) 31 200815878 25623pif

(VIII-5)

(Vlll-6) a base of 3 to 30, or a carbon number of t = two: an independent carbon number of [13 kinds of liquid crystal alignment film" characterized by: liquid crystal as disclosed in (1) to The state of the alignment agent is formed by burning. [14] A liquid crystal display device comprising: a pair of opposite pairs disposed on a side or both sides of a surface on which the substrate is opposed to each other, and a surface facing each other on the substrate The liquid crystal alignment film according to (10) above, wherein the liquid crystal layer is formed between the pair of substrates. (The liquid crystal alignment material of the present invention comprises a composition of a Nadick acid-based v compound, and a polymer component selected from the polyamic acid and the poly-derivative. The poly-acid is made by making four a polymer obtained by reacting diacetyl acid with an amine, dissolved in a solvent, coated on a substrate, and heated to form a liquid crystal hard coat film composed of a polyimide film on the surface of the substrate Examples of such derivatives of poly-proline are soluble polyimine (p〇Iyimide), polyphthalate ((8) oxime and P〇lyamic acid amide. More specifically, Y exemplifies a part of the poly-imine, which is obtained by partially dehydrating and ring-closing the polyamine of the polyaminic acid and the carboxyl group, and the polyacrylonitrile and the polyaminic acid are replaced by 32 200815878 25623pif. a polyphthalamide-polyamide copolymer obtained by reacting a part of a tetracarboxylic dianhydride with a tetracarboxylic acid dianhydride (or a halide or an acid anhydride thereof), and Polyamidoguanidine obtained by partial or complete dehydration ring closure of poly-proline _polyamide copolymer In addition, when the tetracarboxylic dianhydride and the dicarboxylic acid are used as the acid component, not only the linoleamide copolymer but also the polyamine and/or the poly lysine mixture may be obtained. On the basis of this possibility, it is called polyca-acid_poly-silk on the premise of this invention. At least for this kind of derivative, at least one kind of polymer selected from such a derivative is used. Use at least two of such polymers. ==) == Dick acid _ compound

(8) wherein R1 and R2 are independently hydrogen, an alkenyl group having 3 to 6 carbon atoms, an alkyl group having a carbon number of 5 Å, > -'~2 or 2. When the loop wire having 5 to 8 turns and the aryl fresh base η are 1, the ring-burning group having a carbon number a, the carbon number being 6 to 12 = two 2: then 2 to 6 is an anthracene group, and L3 is carbon. The number i is a carbon number of 2 to 6 carbon atoms, R5 is a carbon number, Z is a carbon number, 7 fluorenyl group, B1 is an arbitrary hydrogen, 200815878 25623pif f _〇H substituted phenyl group, B2 is arbitrary The hydrogen can be taken from _〇H, the base of the T^d, _arR, u" field is replaced by -4^3)2-, -CO., -〇-, -s·, An 0 or 1, r is 1 to 30 敕, , a 2-' q is an integer of ... Chuan, and s is 〇 or }. When η is 2, R3 is an alkylene with a carbon number of 2 to 2 〇, a 叙 栌 山 止 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Affinity 6 to 12, 1α 2

-ΟΛ-bW...β2 2 —L _(QV(LH t 士 B _, or -B _〇_B2_C(CH3)rB2-〇

At this time, L], L2, and L4 are independently: 〇7... and L, a sub-alkyl group which is a carbon _, an L-alkyl group, and an anthracene group of 1 to 4, and B2 is independently -0ϋSubstituted phenylene group, τ 芍任心虱2 m 4 丞丄马Ui2" -〇:Οί3)2-, <:〇" Seven... or =2_'q40 or 1, r is 1~ An integer of 30, and S is ο i is a specific example of a dike surface imine compound, which is a compound of the following yak and an oligomer of the following compound k oligomer). N-methyl-allylbicyclo[2.2J]hepto-5-ene-23-dicarboxy imide, ', N-methyl-allyl Methylbicyclo ρ·2·1]hept-5-ene-2,3-di-rebasic imine, N-methyl-mercaptopropyl bicyclo[2·2·1]hept-5- Alkene-2,3-disulfhydryl imine, N-fluorenyl-mercaptopropylidenebicyclo[^ 士 士 ^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Propylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyl

34 200815878 25623pif 醯imino, N-(2-ethylhexyl)-allylmethylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine, N-allyl -Allylbicyclo[2.2.Ϊ]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylhydrazinobicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine, N-allyl-mercaptopropyl bicyclo [2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-isopropenyl-mercaptopropyl bicyclo [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl bicyclo [ 2.2.1] hept-5-ene-2,3-dicarboxyindolimine, ' 'N-cyclohexyl-allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醢iamine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyacid imine, N-benyl-propyl propyl sulphate [2.2. 1] G-5-expansion-2,3-di-supplemental imine, N-phenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine , 35 200815878 25623pif N-mercapto-fine propyl double [2.2.1] G--5-fine-2,3-di-reactive iminoamine, N-benzyl-allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-benzyl-mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(2'-hydroxyethyl)-allyl Bicyclo [2.2.1] heptene-2,3-dicarboxy quinone imine, N-(2'-hydroxyethyl)-allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3_Dicarboxy quinone imine, N-(2f-hydroxyethyl)-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2' , 2f-dimercapto-3'-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2f,2'-dioxin Hydroxypropyl)-allylmethylbicyclo[2.2.1]hept-5-unloaded-2,3_bis-retinylimine, N-(2',3f-dihydroxypropyl)-allyl Bicyclo[2.2.1]hept-5-ene-2,3-di-trans-acid imine, N-(2',3'-dihydroxypropyl)-allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine, N_(3'.hydroxy-indole-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine, Ν-β-hydroxy·cyclohexyl)-allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-di-rebasic , Ν-(4'-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy 36 200815878 25623pif quinone imine, N-(4'-hydroxyphenyl) -allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, hydroxyphenyl)-methylallylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine, N-(4L hydroxyphenyl)-mercaptopropyl hydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (3f-hydroxyphenyl group) allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(3f-hydroxyphenyl)-allylhydrylbicyclo[ 2·2·1]hept-5-ene-2,3-dicarboxy quinone imine, N-(p-hydroxyphenyl)-dilylbicyclo[2.2.1]hept-5-rare-2, 3-di-protective imine, N-{2H2f-hydroxyethoxy)ethylbuallylbicyclo[2.2.1]hept-5- fine-2,3-di-carbamic acid imine, N- {2'-(2L hydroxyethoxy)ethylbuallyl fluorenylbicyclo[2.2.1]hept-5-fine-2,3_disulphonyl imine, N-{2'-(2L Hydroxyethoxy)ethyldidecylallylbicyclo[2.2.1]hept-5-fine-2,3-di-trans-acid imine, Ν-{2'-(2'-hydroxyethoxy)B Keb methallyl fluorenylbicyclo[2·2·1]hept-5- _2,3-di-rebelletic imine, N-[2f-{2f-(2"-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2·2·1]hept-5 -fine-2,3-di-biotinimidate, 1[2'-{2'-(2"-hydroxyethoxy)ethoxy}ethyl]-allylhydryl 37 200815878 25623pif bicyclo [ 2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, !^[-[2'-{2'-(2&quot;-xiang:ylethoxy)ethenyl}ethyl] -methyl propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-{4'-(4f-hydroxyphenylisopropylidene)phenyl}-ene Propylbicyclo[2.2.1]hept-5-fried-2,3-diindenyl iodide, N-{4f-(4f-hydroxyphenylisopropylidene)phenylbuallylmethylbicyclo [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, N-{444f-hydroxyphenyl isopropylidene) phenyldopylallyl bicyclo [2.2.1] g-5- Fine-2,3-dimercaptoimine, N,Nf-ethylidene-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyarminemine: &gt;, Ν, &gt; Γ-ethylidene-bis(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N, Nf-ethylene - bis(decylallylbiscyclo[2·2·1]hept-5-ene-2,3-dicarboxyl醯imino), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), 'N,Nf-hexammine Base-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindolide), N,Nf-hexaindolyl-bis(allylhydrazinobicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-dodedecyl-bis(allylbicyclo[2·2·1]hept-5-ene -2,3-dicarboxy quinone imine), hydrazine, Ν'-taudecyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene 38 200815878 25623pif -2,3-two Carboxylimine), hydrazine, Ν'-cyclohexylene-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine), ..... .....N,N'-cyclohexylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 1,2-double { 3H allyl bicyclo [2.2.1] hept-5-ene · 2,3-dicarboxy quinone imine) propoxy} ethane (1,2-bis {34allylbicyclo[2·2·l]hepto-5 -ene-253-dicarboxy imide)propoxy}ethane ) ^ 1,2-bis{3H-allylhydrazinobicyclo[2·2·1]hept-5-ene-2,3-dicarboxyarmineimine) Oxygen}ethane, 1,2-bis{3H-mercaptopropyl bicyclo[2 .2.1]hept-5-enedicarboxy quinone imine)propoxy}ethane, bis[2'-{3'_(allylbicyclo[2.2.1]hept-5-ene-2,3_ Dicarboxy quinone imine) propoxy}ethyl] scaly, bis[2L{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) Propoxy}ethyl]ether, Μ-bis{3f-(allylbicyclo[2.2.1]heptene-2,3-dicarboxyindolide)propoxy}butane, double {3' -(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyacidimide)propoxy}butyl, N, lsT-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,Nf-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), 39 200815878 25623pif N,Nf-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-m-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,Nf-{(l- Indenyl)-2,4-phenylene}•bis(allylbicyclo[2·2·1]hept-5-fine-2,3-di-rebasic imine), N,Nf-pair Dimethylphenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxy quinone imine), N,Nf-p-diphenylene phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , Nf-m-diphenylene phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), hydrazine, hydrazine m-xylylene-bis(ene) Propyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2.2-bis[4'-{4'-(allylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2.2-bis[4H44 allylmercaptobicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine)phenoxy}phenyl]propane, 2.2-bis[4f-{4'_(mercaptoallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindolide)phenyl}decane, double {4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}decane 40 200815878 25623pif double {4-(mercaptopropyl double ring) [2.2.1]Hept-5-ene-2,3-dicarboxy quinolinimine)phenyl}methyl 3, bis{4-(decylallylhydrylbicyclo[2.2.1]hept-5- Aceene-2,3-dicarboxy quinone imine)phenyl}decane'.... ............ Double {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl} bond, double {4 -(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl}ether, bis{4-(decylallylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine) phenyl}ether, bis{4-(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyfluorene Imine) phenyl} stone wind, double {4-(allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) phenyl sulfone, double {4- (Mercaptopropyl bicyclo [2.2.1] heptene-2,3-dicarboxy quinone imine) phenyl} fluorene, 1,6-bis(allyl bicyclo[2·2·1]g- 5-ene-2,3-dicarboxy fluorene 'amine>-3-light-hexane, 1,12-bis(nonylallylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxy quinone imine)-3,6-dihydroxy-dodecane, 1,3_bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarenimine) -5-light-based-hexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)propoxy}- 3-light base-heptane, 41 200815878 25623pif 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)-2-3⁄4-yl-benzene,1,4-Bis(allyl-decylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)-2,5-di-based-benzene, N,Nf-pair ( 2-hydroxy) stilbene phenyl-bis(allylbicyclo[2·2·1]hept-5-gast-2,3-diindolyl), N, lsT-p-(2-hydroxyl ) xylylene-bis(allylhydrazinocyclo[2.2.1]hept-5-gast-2,3-di-carbamic acid imine), hydrazine, Ν'-m-(2-hydroxy) sub-di Phenylphenyl-bis(allylbicyclo[2·2·1]hept-5-expansion-2,3-di-rebel imine), hydrazine, Ν'-m-(2-hydroxy)xylylene - bis(decylallylbiscyclo[2·2·1]hept-5- fine-2,3-di-supplemental enamine), N,Nf-p-(2,3-dihydroxy)pyridinium Phenyl-bis(allylbicyclo[2·2·1]hept-5-baked-2,3-di-rebase], 2,2_bis[4'-{4|_(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2f_^yl-phenoxy}phenyl]propane, V double {4-(allylhydrazinobicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenyl}decane, bis{3-(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxyindolimine)-4-anilino-phenyl}scale, double {3-(mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylate醯imino)-5-light-phenyl}, 1,1,1_tri{4H allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone )}phenoxymercaptopropane, 42 200815878 25623pif 1^ and, 1^3 (ethylidene methylallylbicyclo[2.2.1]g _5_woman_2 dicarboxy quinone imine) isocyanuric Acid ester. </3> Further, it may be a substance containing an asymmetric alkylene group and a phenylene group. ......................-..........

The above alkenyl-substituted nadic acid ruthenium imide compound may be used singly or in combination of two or more kinds. Examples of the preferred alkenyl substituted nadic acid ylidene imine compounds described above are listed below. N,N,-Ethylene-bis(dipropylbicyclo[2.2.1]hept-5-ene-2,3-dicarbenimide), N,Nf-ethylene-bis(allyl Hydrazinyl double ring II 43 200815878 25623pif carboxy quinone imine), 1 ^ ^ ethylene - bis (methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quin , N, NL, tris-mercapto-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindenine), N,Nf-hexaindolyl-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,Nf-hexaindolyl-bis(allylhydrazinobicyclo[2·2·1]g -5-ene-2,3-dicarboxy quinone imine), N,Nf-dodedecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine), hydrazine, Ν'-taudecyl-bis(allylmethylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine), N, Nf - cyclohexylene-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindenine), N,Nf-cyclohexylene-bis(allylhydrazino) Bicyclo[2·2·1]hept-5-ene-2,3-dicarboxy' quinone imine), &lt; Ν, Ν^ p-phenylene bis(allylbicyclo[2·2·1] Hg-5-ene-2,3-dicarboxy quinone imine), N Nf-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-phenylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,Nf-m-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5 -ene-2,3- 44 200815878 25623pif dicarboxy quinone imine), N,N'-{(1_methyl)_2,4_phenylene bis(allylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-p-xylylene-bis(allylbicyclo[2.2.ί]hept-5-ene-2,3-dicarboxyfluorene Imine), N, Nf-p-diphenylene phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine), N,Nf-inter Xylylene-bis(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindenine), N,Nf-m-diphenylene bis(allyl) Base bisbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), 2.2-bis[4f-{44 allylbicyclo[2.2.1]hept-5-ene-2 , 3_dicarboxy quinone imine) phenoxy} phenyl] propane, 2.2-bis [4'_{4'·(allyl fluorenylbicyclo[2·2·1]hept-5-ene_2 , 3_dicarboxy quinone imine) phenoxy} phenyl] propane, 2, 2 _ double [ 4'-{4'_(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarenimine)phenoxy}phenyl]propane, 'double{4-( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} decane, bis {4-(allyl fluorenylbicyclo[2.2.1] g-5 -ene-2,3-dicarboxy quinone imine)phenyl}decane, bis{4-(mercaptopropyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine Phenyl}methane, double {4-(methylallylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl 45

200815878 230ZJpiI quinone imine) phenyl}methane, double {4-(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, ... double Allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, bis {4-(mercaptopropyl bicyclo [2.2.1] g- 5-ene-2,3-dicarboxy quinone imine) phenyl}, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) benzene }, { {4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl} fluorene, double {4-(decyl allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazomine)phenyl} hydrazine, s Examples of better alkenyl substituted nadic acid ylidene imine compounds are listed below. N,Nf-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 'N,N'-ethylene-bis(allyl) Base bisbicyclo[2·2·1]hept-5-enebiscarbendimimine), N,N'_ethylene-bis(nonylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), N,Nf-triindolyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarenimine), N , Nf-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl 46 200815878 25623pif quinone imine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-dodedecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, hydrazine 12-decyl fluorenyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), wind 1 ^ _ cyclohexylene - bis (allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, Nf- sub Cyclohexyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,Nf-p-phenylene-bis(allylbicyclo[2] ·2·1]hept-5-ene-2,3-dicarboxy quinone imine , N, Nf-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,Nf_m-phenylene_double (allyl bicyclo [2·2·1] heptene 2,3-dicarboxy quinone imine), ' Ν, Ν'-m-phenylene-bis(allylmethylbicyclo[2·2 ·1]hept-5-ene-2,3-dicarboxyindolimine), N,Nf-{(l-methyl&gt;2,4-phenylenebis(allylbicyclo[2.2.1] Geng-5-unloaded-2,3-di-rebornyl imine), N,N'-p-diphenylene phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N, NL p-diphenyl phenyl-bis (allyl fluorenylbicyclo[2.2.1]hept-5-ene 47 200815878 25623pif an enantiomer), N, Nf-m-diphenylene bis-allyl (allylbicyclo[2.2"]hept-5-ene-2,3_dicarboxyarmine), n,nl meta-diphenylene-bis(allyl Indenylbicyclo [2·2· ηheptene-5-ene-2,3-dicarboxyindenine), 2.2-bis[4'-{4'_(allylbicyclo[2.2.1]hept-5 - enedicarboxy quinone imine) phenoxy} phenyl] propyl ketone,

2.2-Bis [4匕{4'-(allylmethylbicyclo[2·2·1]hept-5-ene-2,3-dicarbanyl] &amp;imine]phenoxy}phenyl ]propane, 2.2-bis[4'-{4'_(decylallylbiscyclo[2·2·1]hept-5-ene-2,3-disulfhydrylimine)phenoxy} Phenyl]propane,

Double {4-(allylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindolimide)phenyl}decane, V double {4-(allylhydrazinobicyclo) [2·2·1]hept-5-ene-2,3_bis-sodium iodide)phenyl}zepine, *double {4-(methylallylbicyclo[2.2.1]hept-5 _ene 2,3_didecyl quinone imine) phenyl} decane, 'double { Μ methyl propyl propyl bicyclo [2. zi] i 5 | 2, 3 e s quinone imine) phenyl } decane. ' Soil is a compound (a-3 48 200815878 25623pif

(a-1)

(a-3) The use ratio of such an alkenyl-substituted nadic acid ruthenium imine compound is 0.001 to 5, preferably 0.01 to 2, more preferably 0.05 by weight based on the weight of the polymer component. 〜1·2 若 When the amount of the alkenyl-substituted nadic acid ylidene imide compound of the present invention is within this range, it is possible to maintain a long-term reliability, a liquid crystal alignment property, and a balance between display qualities. Liquid crystal alignment agent varnish. The polymer component used in the present invention is at least one polymer selected from polylysine and derivatives thereof. Further, the polyglycolic acid of the present invention is obtained by reacting at least one of the carboxylic dianhydrides of the formulae (1) to (17) shown below with a diamine. 49 200815878 25623pif

50 200815878 25623pif

Ph. .Ph

(17) In the formulae (16) and (17), ph represents a phenyl group and represents a fluorenyl group. The preferred tetrabasic acid dianhydride used in the present invention is at least one of the compound represented by the formula (Μ) and the compound represented by the formula (17), or the compound represented by the formula (16) and the formula ( 17) A mixture of at least one of the compounds shown and at least one of the compounds of the formula (15). A part of the tetracarboxylic dianhydride used in the present invention may be replaced by the carboxylic acid I. By replacing a part of the tetracarboxylic dianhydride with a carboxylic anhydride, the polymerization can be terminated, and the reaction can be continued to control the molecules of the obtained polymer (poly-acid): =:::: No Any diamine may be used in the 1G «or 】 〇 Λ Λ ί ί 发 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 However, most of the following calves are required: A 3L liquid crystal display element is required to be 8 〇. ~know. Month y · # ^ C pretilt angle ), OCB ^ r, a% ^ # 〜20. The left and right tilt angles, TN face crystal display. In the case of the component, 3 is required. ~10. Left and right tilt = _ LCD display male needle angle, and IPS type liquid 51 200815878 25623pif Due to the green condition of the green member, 0 to 3 can be requested. Smaller tilt angles on the left and right. Therefore, the adjustment of the tilt angle must be considered. Among them, diamines can be classified into two types depending on their structures. That is, when a skeleton linking two amino groups is regarded as a main chain, a diamine having a side chain group in which a radical is branched, and a diamine having no side chain group. By reacting a diamine having a side bond group with a tetra-acid dianhydride, a polylysine or a polyimine having a plurality of side chain groups relative to the main chain of the polymer can be obtained. When such a polyamic acid or polyimine having a side chain group with respect to the polymer main chain is used, the liquid crystal alignment formed by the liquid crystal alignment agent containing the polymer can be used; the inclination angle of the liquid crystal display element can be made large. ~, this side chain group is: and has: the effect of the angle of the group, can be selected from the carbon number is greater than or equal to 3 _ base ^ = equal to 3 octa oxygen, carbon number 3 _ oxy Wei Ke 1 = steroid skeleton The group and the group having a carbon number greater than or equal to 3 = base, Wei Da riding on 3 oxy or having a carbon number greater than #3, 1 filament. In the present invention, a diamine having such a side chain group is referred to as a diamine. The diamine having no such a side chain group is referred to as a non-side bond type 1 amine. Further, the side chain type diamine and the non-side bond type which are appropriately combined correspond to the inclination angles required for each of the above various display elements. #,益可 In the case of a large tilt angle, use at least one of the non-side-bonded diamines =

In the case of a liquid crystal display device, an OLED type liquid crystal display device, or a liquid-type display device, a combination of a TN-type and a side chain-type diamine can be used for two-to-one display. The blending ratio of the type diamine is appropriately selected according to the m-error of the tilt angle of the object, and only the side chain type diamine = 52 200815878 25623pif is used to correspond to the desired tilt angle. Thus, the liquid crystal alignment agent of the present invention can be applied to any type of liquid crystal display element. Specific examples of the side chain group are as follows. First, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkyl carbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group may be mentioned initially. , alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylamine Alkylcarbonyl and the like. Further, the alkyl group, the alkenyl group and the alkynyl group in these groups are all groups having a carbon number of 3 or more. Among them, in the alkoxyalkyl group, the total carbon number is preferably 3 or more. Further, these groups may be linear or branched. f times, the terminal ring has an alkyl group having a carbon number of 3 or more, a carbon number of 3 &amp; an oxy group or an alkoxyalkyl group having a carbon number of 3 or more as a 3 group = a phenyl group, a phenyl group Recorded, phenyl alkoxy, benzene t benzene; Qiao base phenyloxy, phenoxy woven, phenylamine group n 1 number is greater than #3 ring filament, cyclohexyl burning ^ 2 m hexyl oxygen _, cyclohexylphenyl, cyclohexylphenyl bis(cyclohexyl)phenyloxy, bis(cyclohexyl)fluorenyl, yl, bis(cyclohexyl) benzyl, bis(cyclohexyl) A group having an oxy group of the same ring structure. The hexyloxy group can be used not only by a single bond, but also by a bis(phenyl group). Alternatively, it can be a group of 2, respectively, which may be bonded by a sub-alkyl group. A single bond, -0-, _C0 (^ * or more than 2 benzene rings or cyclohexyl rings via 〇C〇_, _c〇nh_ or a carbon number of 1 to 3, the ring of the 200815878 25623pif end has a carbon number greater than An alkyl group equal to 3, a carbon-fluorine-substituted alkyl group, a carbon number of 3 or more, or a large number of gorges in the 3 眺 眺 作 作 骑 骑 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举Good example. h2n - a1-nh2 one (丨) Γ\ Η2Ν ν一^ΝΗ2 (II)

(III) (IV) (V) nh〇

(VI) (VII) In the formula (I) to the formula (VD), a1 is a linear alkylene group having a carbon number of 2 to 12, and A is a number of 1 to 1; a linear alkylene group of 2; A3 Independently, single bond, face 〇·, -CO-, -C0NH ...WHC0 ...-C(CH3)2-, -C(CF3)r, -0-A2H-, each S--S〇2...each A2 Or a linear alkylene group having a carbon number; any hydrogen of the cyclohexane ring and the benzene ring may be substituted by fluorine, -CH3, -OH, -C00H, s〇3H, p〇3H2, benzyl or hydroxybenzyl . 54 200815878 25623pif Examples of the diamine represented by the formula (I) are the compound (I-1) to the compound (I-4). H2N(CH2)2NH2 H2N(CH2)4NH2 H2N(CH2)eNH2 H2N(CH2)12NH2 ........(1-1)... (I-2) (Bu 3) (Bu 4) Formula (Π Examples of the diamines which are not present are the compound (Π-1) and the compound (Π-2). η2νΗ^}-νη2 (ΙΜ) (Π-2) Examples of the diamine represented by the formula (m) are the compound (m-1) to the compound (m-3).

An example of the diamine represented by the formula (IV) is a compound (IV-1) to a compound (IV-16) 〇 h2n (IV_1)

(!V-6)

55 200815878 25623pif

An example of the diamine represented by the formula (V) is a compound (V-1) V-34) 〇

-nh2 H2N

Nh2 h2n (V-2)

(V-3) (V-1)

(V-12) (V-13) 56 200815878 25623pif

(V-14)

NH2 (V-15) (V-17) (V-16) (v·18) (V-19) H2N~{^Sx&lt;Q&gt;-NH2 (▽•20) (V-21) h2n-^&gt ;~ss-^^~nh2 h2n-^ksvS^&gt;-NH2 (V-22) (V-23) h^-^s^s^〇~nh2 h2n-〇&quot;s^^s-〇- Nh2 « (V-24) (V-25) h2n-Q/s^-s^-nh2 h2n^s^^s^nh2 (V-26) (V-27) 57 200815878 ,25623pif

NH2 h2n NH2

(V-31)

(V-32)

An example of the diamine represented by the formula (VI) is the compound (VI-1) to the compound (VI-6).

(VI-5) (VI-6) An example of the diamine represented by the formula (W) is a compound (W-1) to a compound (W-16) 〇 58 200815878 • 25623pif

(VII-7) (VII-8) _~〇^〇2〇^called H2N-Q^〇^f H2N~〇&quot;0v〇^ch

(VI1-13) (VII-14)

/&gt;—nh2 h2n (VI1-15)

(VII-16) More preferred examples of the above diamine are the compound (IV-1) to the compound (IV • 5), the compound (IV to 15), the compound (rv-16), and the compound (v Ο~ compound ( V-20), compound (V-26), compound (V27), compound (V-31), compound (VI-1), compound (VI 2), compound (γι-6), compound (Υ[ [1) ~ Compound (grab one) ' Particularly good examples are compound (IV-1), compound (IV-2), chemical 59 200815878 25623pif compound (IV^-15), / human / compound (V -13), to 16), compound (V-1) compound (W~2) ° compound (er ===. compound core and required voltage retention rate ~, ratio 艮: selected diamine The mol% of the mechanism, the better η 5仏 week can be completed, the rut is good 1 mol% ~ 1 〇〇 and the wild 疋 5m 〇 1% ~ 8 〇 m 〇 1 〇 / 〇. As mentioned above' In the present invention, at least a VA type liquid crystal display element-type diamine is used, especially in the display element, and the STN type liquid crystal side chain type diamine. X large tilting type or the like is preferred. It is preferred to use an amine side chain type diamine. ~ Pounds of formula (v) the user is shown the formula (Shan) bis

(VII!) = Medium 'R6 is a single bond, orphan, _C()Q, _(four), _c 〇, 2 CF2〇-, or an alkylene group having a carbon number of 1 to 6, which is an arbitrary alkyl group. CHr may be substituted by _〇_, Γ ^ υ7 H-CH'_feC_; R7 is a group having a steroid skeleton, and an alkyl group having an inverse number of 3 to 3 Å, having a carbon number of 3 30, An alkyl group or an alkoxy group having a number of 3 to 3 Å as a substituent or a group represented by the formula (D, 丨), and any -CH2- of the alkyl group may be -0-, -CH = CH- or substituted. 60 200815878 25623pif

(D-1) wherein 'R'8, Rl9 and R2G are independently a single bond, 〇_, c〇ri -OCO-, -CONH·, a sub-wire having a carbon number of 4, an oxy-indenyl group, or a carbon The number is a siloxane; the independent of fj1 is 1&gt;4 phenylene or M_cyclohexylene; r2] and r or methyl, ml and m2 are independently 〇, u2; e, f" 》 The integer of ～3, the total of e, f, and g is greater than g: the number is 3~ ing, the number of charcoal is 3~3〇, 1, 1: is carbon~祁 p p I I 兀 兀, or A cyclyl group having a carbon number of 3%, which has a base, a base: 'any hydrogen can be replaced by a ruin, and any .CH2 can be substituted by a group represented by a =j group or a formula (D-2). R26 'Si·k〇-Si— I \ I R25 \ R27 R24 (D-2)

(IX)

Wherein NH 2 is 1 to 30, wherein R 8 is independently hydrogen or methyl; R 9 is hydrogen; carbon number 61 200815878 25623 pif alkyl, or carbon charcoal, -CO · or _CH is 2 to 3 〇; And, f is independent

1-0—〇-rV R12“, V is independently hydrogen or methyl; R9 is hydrogen, (X) is a burnt group, or carbon is stupid: nuT is 1~30, and the number is 2~30. R10 is independently a single bond, and R11 and R12 are independently hydrogen, carbon number based, or alkane 3〇 alkane r13-KSh

R R 14

C 14

In Nhl·(XI)-rai, the 2' J of the alkyl group having a carbon number of 3 to 3 Å is substituted by -CL, _CH=CH_4 C is C-C; the carbon number of Rl4 is 1~ 6 alkylene; ring A is 1, 'phenylene or 1, base, & is 0 or 1; b is 0, 1 or 2; and, c is independently 〇 or ^.

H2Nv/=\ / x p15 \

(xii) ', Zhonghan is a carbon number of 3~3〇 or a hindrance of 3 &gt;alkyl; R36 is hydrogen, carbon number is 30 alkyl, I carbon bomb is two 62 200815878 25623pif A fluorinated alkyl group; R17 is independently -O- or an alkylene group having 1 to 6 carbon atoms; and, d is independently 0 or 1.

(Vlll-3) An example of the compound (M) is shown below. H2n h2n h2n

(VIII-1)

(VJII-2) -R28 &lt; V-R28 &lt; V^r29

R 28

(vm-6)

R 28

(VIII-11) In the formula (M-1) to the formula (W-11), R28 is an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, preferably having a carbon number of 5 to 25 alkyl groups or alkoxy groups having 5 to 25 carbon atoms. R29 is an alkane having a carbon number of 3 to 30. The group is alkoxy group having a carbon number of 3 to 30, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

(VII) (VIII-17) In the formula (M-12) to the formula (M-17), R30 is an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. . R31 is an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms.

(VIII-22) (VI11-23) 64 200815878 25623pif 32

(Vlli-34) H2N 〇 R32 , 33 (VIII-36) 33

CH3 ch3 II Si—Ο-Si—RII ch3 ch3 65 32 200815878 25623pif In the formula (W 18)~ (Μ—37), R32 and R33 are independently a carbon group having a carbon number of 3 to 30, or a carbon number of The alkoxy group of 3 to 30 is preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. ...........

Among the above compounds, preferred are the compound (Μ-1) to the compound (Μ-11), more preferably the compound (Μ-2), the compound (Μ-4), the compound (砸-5), and the compound (Shen One 6). In the formula (Κ), it is preferred that two of the two "NH2-(Ph&gt;R1G-〇-" 66 200815878 25623pif one bond to the 3 position of the steroid nucleus and the other bond to the 6 position. With respect to the bonding position of R](), it is preferred to bond to a meta position or a para position. Examples of the diamine represented by the formula (IX) include a compound (K-1). ~ Compound (IX-4).

In the formula (X), the bonding position of the two "NHH:R12-)(Ph)_R1C)-0-" with respect to the benzene ring is preferably a meta or a pair with respect to the carbon to which the steroid core is bonded. Bit. The bonding sites of the two amine groups with respect to the benzene ring are preferably meta or para to R1G, respectively. An example of the diamine represented by the formula (X) is a compound (X-1) to a compound (X-8) 〇 67 200815878 25623pif

68 200815878 25623pif

69 200815878 25623pif In formula (XI), the preferred bonding position of the two amine groups relative to the benzene ring is meta or para position relative to R14. An example of the diamine represented by the formula (XI) is a compound (XI-1) to a compound (XI-8) ° R34 R34

(XI-4) R35

(XI-5) 70 200815878 25623pif R35

In the formula (XI-1) to the formula (XI-8), R. 4 is a burnt group having a carbon number of 3 to 30. R is a burnt group having a carbon number of 3 to 20. In the above formula (XH), the preferred bonding position of the two amine groups with respect to the benzene ring is a meta or para position with respect to R17. A preferred example of the diamine represented by the formula (M) is the compound (Μ-1) to the compound (XH-3). 71 200815878 25623pif

Or 'R in the above formula. 6 is a burning group having a carbon number of 6 to 20, and r37 is an alkyl group having a carbon number of 1 to 10. …disaster

The compound (observation) to the compound (observation) may be used alone or in combination of two or more. The ratio of the compound (m) to the compound (M) in the total amount of the diamine may be adjusted according to the selected two desired tilt angles, preferably lm 〇 1% to 1 〇〇 m 〇 i%, more preferably It is 10 mol% ~ 1 〇〇 mol%. The compound (m) to the compound (observation) is preferably a compound (M-2), a compound (Shen-4), a compound (Fig. 5), and a compound (M-6). mouth \

Wherein, and E29 is independently an alkyl group having a carbon number of 3 to 3 Å or a carbon number of 72 200815878 25623pif is an alkoxy group of 3 to 30 Å. In the present invention, it is preferred to use a diamine selected from the compound (I) to the compound (W) in combination with a diamine selected from the compound (er) to the compound (M). Further, it is particularly preferred to use a mixture of the compound (IV-1), the compound (IV-2), the compound (IV_15), the compound (IV_16), the compound (V-1) to the compound (v-13), and the compound- 2) A mixture of at least one selected from the group consisting of at least one selected from the group consisting of a compound (Shan-2), a compound (Shan-4), a compound (View-5), and a compound (Shen-6). Further, the proportion of the diamine selected from the compound (Shan-2), the compound (Fig. 4), the compound (Fig. 5), and the compound (M-6) in the total amount of the diamine is preferably 1 〇mol% ' is better 30 m〇l%~100 m〇1%. Further, as the diamine in the present invention, the other diamines of the compound (I) to the compound (synthesis and the compound (5) to the compound (five) can be used. Here, the hemi 4 can be any diamine, for example, it can be cited as having a Cai a naphthylamine having a structure, a g彳-, a diamine having a first structure, or a diamine having a side chain structure having an oxygen-suppressing bond. (5) a nonoxylane-based diamine other than the compound (5) is not particularly It is defined by the following formula (XV). (4) Using H2N-fA4)

(XV) /, wherein R and R are independently a decyl group or a phenyl group having a carbon number of 3, and 73 200815878 1 is a phenylene group substituted with a methyl group, a phenylene group or a warp group. The number of turns, m is an integer of 1 to 1 。. use'. ΐ 1 1 is not particularly limited. In the present invention, it is preferable to make the F-type (Γ) to the formula (8,).

V /~nh2 h2n fly, _ (2')

The diamine in the invention of the present invention can be imparted with a preferred tilt angle from the liquid crystal alignment formed by using the liquid crystal alignment agent of the present invention by appropriately selecting the kind of the diamine and the two. ~, a part of the diamine in the invention can be replaced by a monoamine. By replacing the second, anti-employment fraction with a monoamine, the polymerization reaction can be terminated, so that the handleable CH i can easily control the obtained polymer (polyglycine). The ratio of the early amine to the diterpene is preferably within a range which does not impair the effect of the invention of 4 74 200815878 25623pif, so that the total amine is 10 m 〇 1% or less. 1 〇 1% of the female or the poly-proline and the derivative thereof in the present invention may have any weight average molecular weight. The weight average molecular weight of the above polylysine and its derivative is not particularly limited, and it is preferably used as a liquid crystal alignment _ component, preferably greater than or equal to 1 x l 〇 4. greater than or equal to: 3 The weight average molecular weight poly-proline and its derivatives do not evaporate in the step of roasting the liquid crystal film, and have the same as the liquid crystal alignment agent: the weight average of the polyaminic acid and its derivatives. The molecular weight is determined by gel permeation chromatography (GPC), for example, by diluting the obtained polylysine and its derivative with dimethylf〇rmamide (dmf) to make polyfluorene. The concentration of the amine acid was about \ wt%, and it was measured by gel permeation chromatography (Gpc) method using Chromatopack C_R7A (manufactured by Shimadzu Corporation) using DMF as a developing solvent, and was obtained by polystyrene conversion. In the weight average knife, in order to accurately measure GPC such as polyacrylic acid or polyacrylic add, the phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid may be dissolved in the DMf solvent. A developing solvent for an inorganic salt such as an inorganic acid or a lithium bromide or a lithium chloride. The polyacrylic acid and the derivative thereof in the present invention can be produced by a known method, for example, a raw material inlet, a nitrogen gas inlet, and a nitrogen inlet. In a reaction vessel of a thermometer, a scrambler, and a condenser, at least one of a desired amount of a diamine represented by the formula (I) to the formula (XU) is added, and according to the situation of甘从—^· · Next,

Into the required amount of about 1.1). Further, at least one of 2 to fluorenone or dimethyl phthalamide, and tetracarboxylic dianhydride, and further, a carboxylic anhydride is added as needed. At this time, the total amount of tetra dianhydride is preferably equal to the total number of moles of the diamine (the molar ratio is 〇·9~ Γ, under stirring, at a temperature of 0 ° C to 70 ° C The reaction is carried out for 1 to 48 hours, whereby the poly-_Nu can be obtained. The reaction temperature is raised (for example, 5〇t~8〇t), whereby the polyamine having a smaller molecular weight can also be obtained. Poly-proline, which is made up of a large number of poor solvents, and is completely separated from the solvent by filtration, infra-red (Infrared)

Spectroscopy 'IR> and nuciear magnetic resonance (NMR) were analyzed to identify them. Further, the solid poly-proline is decomposed by an aqueous solution of a strong alkali such as kqh or NaOH, and then extracted with an organic solvent. 'G'as chromatograph (GC), high performance liquid chromatography' (high performance) A liquid chromatograph (HPLC) or Gas Chromatography-Mass Spectrophotometer (GC-MS) was used for analysis, whereby the monomers used were identified. The obtained solution of polylysine can be diluted with a solvent to adjust it to a desired viscosity. When the poly-proline in the present invention is a poly-proline derivative, that is, a soluble poly 76 200815878 25623pif yttrium, a poly-proline solution and acetic anhydride or propionic anhydride as a dehydrating agent can be used. ), an acid needle such as trifluoroacetic acid anhydride, and a tertiary amine such as triethylamine, acridine (an oil addition) or dimercaptopyridine (c〇Uidine) as a dehydration ring-closing catalyst together at a temperature of 2 (Γ( : ~ ΐ 5 〇 下 under the imidization reaction can also be obtained. Can also use a large number of poor solvents (meth (methan〇1), ethanol (ethanol), isopropanol (is〇pr〇pan〇; [) and other alcohols ( 〇〇h〇i) is a solvent or a glycol solvent, and the polylysine is precipitated from the polyaminic acid solution to precipitate the polylysine in toluene (xylene) and xylene. -e) A solvent such as the above-mentioned dehydrating agent and a dehydration ring-closing catalyst are obtained by a ruthenium imidization reaction at a temperature of 20 C to 150 ° C. In the above hydrazine imidization reaction, the dehydrating agent and the dehydration ring-closing contact are obtained. The ratio of the medium is preferably 0·1~10 (Mo Erbi). The total amount of the two is better than the The total amount of the acid dianhydride contained in the tetracarboxylic dianhydride used is 1.5 2 Torr. By adjusting the chemical hydrazide dehydrating agent catalyst 1, the reaction temperature, and the reaction time, The degree of ruthenium iodization can be controlled to obtain a partial polyimine. Further, as described above, a part of the acid dianhydride used in the tetracarboxylic dianhydride of the present invention can be replaced with an organic dicarboxylic acid. When the polydiamine acid of the present invention is produced by using an organic dicarboxylic acid and a tetracarboxylic dianhydride, a poly-proline-polyamine copolymer can be obtained, wherein the ratio of the organic diwei to the tetracarboxylic acid dihepatic, Insofar as the effect of the present invention is not impaired, it is preferred to have a particle size of 1 〇 mol% or less. Further, the polyglycolic acid-polyamine copolymer can be chemically synthesized. The present invention relates to a liquid crystal alignment agent which preferably contains a solvent, from the viewpoints of adjustment of physical properties such as viscosity, ease of handling, and simplification of the process. And further, the liquid crystal alignment agent contains _. In the liquid crystal alignment agent, the coating method of the liquid crystal alignment agent containing the liquid crystal alignment agent on the substrate is selected. For example, the printing machine used in the manufacturing process of the liquid crystal display element (including the offset printing machine) (offset press) and inkjet printer (the content of poly-proline in the liquid crystal alignment agent of 尬舛k is "Wt%~30 wt%, more preferably! wt%~15 wt%. (4) The solvent can be appropriately adjusted in relation to the viscosity of the liquid crystal alignment agent (described later). The solvent used in this product includes a wide range of production conditions such as poly-acid and dimerizable polyimine. The solvent to be used 'is appropriately selected depending on the purpose of use. The preferred hydrazine of this solvent contains 1) relative to polylysine or a miscible solvent, A2) to modify the enthalpy. Look for:,,,, the solvent mixture of the purpose of the solvent. These solvents are exemplified as non-mass such as N-methyl-tf (hereinafter referred to as aprotic polar organic solvent) which is a good solvent for the raw solvent-soluble polyimine: Example: pyrrole-, di-decyl imidazoline Ketone (dimethyl πη«η〇η〇, 凡methyl caprolactam c-_), 1 曱-amine (7) delete (four) face), 78 200815878 25623pif N,N-dimercaptoamine (n Dimethyl acetamide), dimethyl sulfoxide, N-dimethylformamide, N,N_:ethyl 曱酉m month female ethyl ethyl hydrazine &amp; month female, butyrolactone (γ -butyrolactone), γ-valerolactone (y_valerolactone). More preferably, these are exemplified by Ν_曱ylpyrrole, dimethyl (tetra) 嗤 _, γ _ 内 g γ, γ • pentane vinegar, and the like. /2) A solvent (hereinafter referred to as another solvent) for the purpose of changing the surface tension, improving the coating property, etc.: for example, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin (tetralin), isophorone (isoPh〇rone), ethylene glycol monobutyl ether (ethyl (10) curry im嶋b_ ethei), such as ethylene glycol-based, diethylene glycol monoethyl ether, etc. Ethyl ether, ethylene glycol, monofilament, methyl ketone, ketone, triethylene glycol monobutyl sulphate, propylene glycol monobutyl propyl H monofilament ether, malonic acid diethyl ester (five) malonate, etc. Dipropylene glycol monoalkyl ether such as ester or dipropylene glycol monomethyl ether, or an ester compound such as these acetates. More preferably, it is not ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether or the like. — The type of non-pen-polar solvent and other solvents should be appropriately set in terms of ‘ and ratio, and the printability, coatability, solubility, and storage stability of the liquid crystal alignment agent. The aprotic polar solvent tends to be relatively excellent in competability and storage stability as compared with other solvents, and has excellent printability and coatability in other solvents. As described above, the liquid crystal alignment agent of the present invention may contain various additives. Various additives may be selected from the use of polyamic acid and polymer compounds other than the biologically active or low molecular compound depending on the purpose.叮 79 200815878 25623pif For example, a soluble polymer can be added to a soluble polymer in an organic solvent; Peng =: electrical properties and alignment of the alignment film. This 吝 v 成 / 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 _ (silicone) modified polyurethane, anthrone modified polyester, etc. In addition, the addition of low-molecular compounds, the use of surfactants to meet this purpose can be used when the σ υ 提升 提升 提升 提升 , , , , An antistatic agent is used for electrical properties, and 3) · Lifting and base (4) adhesion or rubbing resistance can be used when using Shi Xitong coupling agent or Cui Tai coupling agent. In addition, 4) 醯 at low temperature A ruthenium-based catalyst can be used for imidization. Examples of the above decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, and (2-aminoethyl)-3-aminopropylmethyldimethoxy decane. N-(2-Aminoethyl) 3-aminopropyl decyltrimethoxy decane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxy oxime, m-amino group Phenyl trimethoxy decane, m-aminophenyl triethoxy oxime, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, 3-glycidoxy 3-glycydoxy propyl trimethoxy silane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrioxane Baseline, 3-chloropropylmethyldimethoxy decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxy decane, 3-mercaptopropyltrioxane Baseline, N-(l,3-dimercaptobutylene)-3-(triethoxydecyl)-1-propylamine, N,N!-bis[3-(tridecyloxydecyl) )propyl]ethylenediamine, etc. 80 200815878 25623pif Examples of the above ruthenium-based catalysts, compared with amines and tripropylene 'Tributylamine and other fat trimethylamine 'triethyl (N, N_dimethyl, e), (d), di-KN-dimethylaniline aniline, substituted phenylamine, etc., amine, methyl substituted Substituted pyridine, hydroxy substituted pyridine, pyridene, methyl substituted quinoline, hydroxy substituted sore 1, quinoline, substituted isoquinoline, substituted by hydroxy , isoquinoline, imidazole methyl substituted by methyl group, substituted by hydroxy group = imidazole, medium, especially scalar N, N-1 silk saddle cyclic amines such as aniline, quercetin, _ Base J~, the present amine, m-pyridine, isoquinoline, etc. The amount of the dipyridylpyridinium or p-hydroxypyridinium coupling agent is usually 0 to 0.1, preferably (4). The amount of the heavy imidization catalyst added to the composition of the cockroach is usually 0.01 to 5 equivalents relative to the carbonyl group of the living organism, preferably 〇: 〇::3 amine = and the addition of other lion additions According to the difference of the materials thereof, the weight ratio of the polymer component is not 相对~〇3, ^~〇1. .3, preferably 0._ The liquid crystal of the invention The viscosity of the agent varies depending on the coating method, the concentration of poly-aracine and its derivatives, the type of polyamine acid and its derivative used, and the type and ratio of the solvent. For example, coating with a printing machine It is preferably 5 mPa·s to 100 mPa·s (more preferably 丨〇mpa s~80 mPa.s). If less than 5 mPa.s, it is difficult to obtain a sufficient film thickness 'if more than 100 mPa · S, There is a case where the printing unevenness is increased. It is preferably 5 mpa · S~2GG mPa · s when it is applied by spin coating, coating 81 200815878 25623pif ^ ^ C°at (better 10 is as~) 100mPa.s). The viscosity is determined by the viscosity measurement method, for example, a viscometer (measured by the machine pendulum D manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25. 〇. 办芬二明之/夜晶配纲 other good form A group (grouP) which is a composition of two or more polymers selected from polyamine 2', which is selected from the group of organisms, is a tetrahydro acid dianhydride and self-chemical II) a non-side chain type diamine selected from the compound (observation), a poly-aramidic acid or a derivative thereof (polymer component A). In addition to the compound I) to the compound (VH), a compound may be used in combination ( Σ ) ~ 5 substances (XU) m Bu diamine. The liquid crystal alignment film formed by using a liquid crystal compound containing a polymer component 可 can impart a good voltage holding ratio to a liquid crystal display element including the liquid crystal alignment film. The other group of the polymer is a polyamic acid or a derivative thereof (polymer component B) obtained by reacting a tetracarboxylic dianhydride with a side chain type diamine selected from the compound (observation) to the compound (M). . "In addition to the compound (observation) to the compound (χιι), a diamine other than the compound (I) to the compound (orphan) may be used in combination. A liquid crystal alignment film formed using a liquid crystal alignment agent containing a polymer component Β has a tilt angle of four liquid crystal display elements containing the liquid crystal alignment film. The other group of the polymer is a poly-proline or a derivative thereof (polymer component C) obtained by reacting tetraruthenic dianhydride with a mixture of the above-mentioned non-side chain type diamine and side chain type diamine. In addition to the compound (I) to the compound (orphan), a diamine other than the above compounds may be used in combination. 82 200815878 25623pif In the present invention, it is preferred to use at least two polymers selected from the polymer component A, the polymer component B, and the polymer component C in combination. For example, in the case of mixing the polymer component A with the polymer component B, the mixing ratio of these polymers is A/B = 99/l to 50/50, and a better ratio is mango = tear to zero. This weight ratio is appropriately adjusted in accordance with the obtained inclination angle, and the inclination angle can be increased by increasing the ratio of the polymer component B. The polymer component C is preferably a combination of the polymer component B and the polymer component a, and the mixing ratio thereof is the same as described above. Further, any of the polymer component A, the polymer component B, and the polymer component c is preferably composed of a plurality of polymers. Further, the liquid crystal alignment agent of the present invention may further contain a polymer component A, a polymer component B, and a polylysine other than the polymer component c. The liquid crystal alignment film of the present invention is a liquid crystal alignment film formed by firing the above polyamic acid in the liquid crystal alignment agent of the present invention in the state of the film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film may be formed by, for example, coating a substrate for a liquid crystal display element, or a substrate for measurement such as calcium nu〇ride or shixi (along 11) The liquid crystal alignment agent heats the film of the liquid crystal alignment to η ϊ ϊ to, for example, 150 C to 40 CTC, preferably 1 g 〇 ° c to 280 ° C. The film thickness of the liquid crystal alignment film is preferably from 1 〇 nm to 3 〇〇 nm, more preferably from 30 nm to 100 nm. Further, it is preferred to subject the liquid crystal alignment film to rubbing treatment. The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid crystal alignment agent or the coating method of the liquid crystal alignment agent. This film thickness can be measured by a well-known film 83 200815878 25623pif thick measuring device such as a profllometer or an ellipsometer (dlips (10) eter). Further, the components in the liquid crystal alignment film can be subjected to hydrolysis or the like as needed, and can be analyzed by a usual analysis method such as IR4MS. The liquid crystal display device of the present invention comprises: a pair of substrates disposed oppositely, 2) a liquid crystal alignment film of the present invention formed on a surface opposite to each of the pair of substrates, and 3) a substrate held between the substrates Liquid crystal layer. The substrate facing the _---electrode is preferably a transparent substrate (e.g., a glass substrate). An electrode is provided on the surface of at least one or both of the substrates on the substrate in accordance with the state of the liquid crystal display element (four). If the above electrode is an electrode formed on S of the substrate, there is no particular jr determination. Examples of such an electrode include steel = oxide (five) ium tin 0xide, IT 〇), or steaming of a metal. The = pole is formed on the base (four) whole surface, and may be formed, for example, as a pattern. On the substrate which is not provided, on the surface of the substrate, 2 = read crystal matching (10), as described above on the substrate on which the electrodes are provided. The formation of the liquid crystal alignment film of the handle of the liquid crystal layer containing the liquid crystal is contained in the liquid crystal layer. The constant anisotropy is a positive composition of any of the night crystal compositions. AI, tropism is | This is a good example = the case of the invention reveals - the bulletin, the _ special table 2 = 84 200815878 25623pif material 1157826, the Japanese patent special Kaiping δ - 23i96 艮 艮 Japanese patent 4 inch Kaiping 9- Japanese Patent Publication No. 241644 (Ep 885272A1), Japanese Patent Laid-Open Publication No. Hei 9-302346 (Ep8〇6466A1), Japanese Patent No. 8-68 (10) 722998Ai, Japanese Patent No. 2: No. 9-235552, Japanese Patent Laid-Open No. 9 —255956号 1 Japanese Patent Unexamined 9-2 Side 3 Bulletin (E Gang (7) Chuan, No. 1204-01616 (Ep 844229ai), 曰 / 2^1 - Chest No. 6 1〇- Patent Specials οι: This patent is published in the publication No. 2〇00-087040, 曰本寻刊%Open 2001-48822, etc. In the VA type liquid crystal display element, the constant anisotropy is negative, and the various liquid crystal groups == The composition can be disclosed in Japanese Patent Laid-Open No. 1 liquid crystal composition, and the Japanese Patent Publication No. 8-409^3 fv 224885 '104869, 3唬Bulletin, 曰本专利特开平8 — This patent is open to the public, No. 6 bulletin, day 236989, public interest ^ ^ Tiger A Newspaper, Japanese Patent Special Kaiping 10 — This Patent _ 1G — _ _, 曰 2 Conference Bulletin, Japan Special Patent This Patent Kaiping 10 — This Patent _ Ping 1Q — 2 Delete = 236994 Bulletin, 曰 23鸠No., Japan=, Japanese material_Ping 10 — This patent is open to the public notice No. 24, Japanese No. 237075, H, Japanese patent special Kaiping 1〇 — 曰本细寸开平1Q—Lei 6 bulletin, day 85 200815878 25623pif Patent Special 1 () ^ Private Report (EP 967261A1), Japan 287 = French Bulletin, Japanese Patent Special Open H) - Tai I #u Bulletin, Japanese Patent Laid-Open No. 10-291945, Japanese Patent Unexamined U - 0295W % u newspaper, day __n i = newspaper, Japanese patent special Kaiping 11 - newspaper 曰 专利 专利 2000 2000 2000-256307 bulletin, 曰 专利 patent 4 inch open 2001~019965 bulletin, 日太哀刹# bulletin:曰 专利 专利 专利 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四Tens of ice Thin has other components. For example, in the TFT type liquid crystal element in which τ巴录1 is not used, the first read 昍i image: fi溥Ϊ transistor, insulating 臈, protective film, signal electrode to: ί'Γ圣寺' brother 2 transparent The substrate may have light outside the blocking pixel area = moment _. It is called a color filter (= 坦 驭 and pixel electrode, etc.) 干 ) ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明The method of the following steps is as follows: 1) cold m on the above two transparent substrates, (10) required to equip the ship water and the reaction required for the reaction, the process of the treatment, and 4) the alignment of the alignment film obtained by the alignment treatment, 5 ) ϋ 86 200815878 25623pif The step of sealing the liquid crystal between the substrates after bonding the two substrates, or the step of laminating the liquid crystal on one of the substrates and bonding the other substrate. The coating method in the step of applying the above liquid crystal alignment agent is generally known as ..................................., ... - . - .. ... has a spinner method, a printing method, a dipping method, a dropping method, an ink jet method, and the like. These methods can also be applied to the method of the above-described drying process and the heat treatment process required for the dehydration reaction in the present invention, and a method of heat treatment in an oven or an infrared furnace is generally known. A method of performing heat treatment on a heating plate (h〇t pIate). These methods can also be applied to the present invention. The drying step is preferably carried out at a relatively low temperature (5 Torr and 140 C) within the range in which the solvent can evaporate. Preferably, the heat treatment step is carried out at a temperature of about 3,000 ° C or so. The alignment treatment of the liquid crystal alignment film is performed on an IPS type liquid crystal display element, an OCB type liquid crystal display element, a liquid crystal display element, and a clear liquid crystal

The rubbing treatment is usually performed. In the VA type liquid crystal display element, there are many cases of processing, but it is also possible to perform rubbing treatment. The board, wherein the substrate is coated with an adhesive and then bonded to another base, and the night, the liquid crystal. In the case of the drop-filling method, the liquid helium is dropped onto the substrate in the bonding month J, and then bonded to the other layer, and the ultraviolet rays are used to harden the adhesive used in the bonding. element. Liquid of the invention of the present invention The liquid crystal wavelength plate and the light-scattering film of the present invention may be a polarizing plate (polarizing film) or a driving circuit. 87 200815878 25623pif [Embodiment] Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples. In addition, the materials used in the examples are shown below. In addition, the unit milliliter of capacity is indicated by the symbol 111]^. [Tetracarboxylic dianhydride] Compound (1): pyrymellitic dianhydride Compound (7): 1,2,3,4-cyclobutane tetracarboxylic dianhydride compound (8) : 1,2,3,4-butane tetracarboxylic dianhydride compound (16):

3,3|,4,4 oxadiphenyl ether tetraphthalic acid dianhydride: 〇〇? 八( '[diamine] ' compound (V-1) : 4,4,-diaminodiphenylmethane compound ( V — 13 ) : 4,4,-diaminodiphenyl ether compound (W-2) : i,3-bis(4-aminophenylphenyl)propane compound (M-2—1): ι, 3_Diamino _5_(4-hexadecylbenzyl) benzene compound (WI-5-1): lv3_diamino-5-(4-(4-(4-pentylcyclohexyl)cyclohexyl) Phenyl)T-phenyl-benzene 88 200815878 25623pif [Alkenyl substituted imidic acid imide compound] (a-1):

(a-1) 〇 〇 This compound is BANI-M available from Maruzen Petrochemical Co., Ltd. ί Compound (a - 2) ··

P 0

(a-2) n-ch2^^ch2-n This compound is BANI-X available from Maruzen Petrochemical Co., Ltd. Compound (a-3):

(a-3) This compound is BANI-H available from Maruzen Petrochemical Co., Ltd. [solvent]

N-mercapto-2-pyrrolidone·· NMP butyl cellosolve (ethylene glycol monobutyl ether): BC γ-butyrolactone: BL &lt; 1. Synthesis of polylysine &gt 89 200815878 25623pif [Synthesis Example 1] To a 100 mL four-necked flask equipped with an aiL meter, a stirrer, a raw material input port, and a nitrogen inlet, 3.995-free compound (observation _2_1) and 60.0 g of dehydrated NMP were added to dryness. Stir and dissolve under a nitrogen stream. Then, 2.042 g of the compound (1) was added, and the mixture was allowed to react at room temperature for 3 hours. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 70 C or less to carry out the reaction. To the obtained solution towel, 34. Q g of BC was added to obtain a poly(acid) solution having a concentration of 6 wt%. This heteroamine was recorded as PA1. The weight average molecular weight of PA1 is π(8)〇. The obtained polylysine is diluted with a (hetero/DMF = G.6_: weight ratio) diluent so that the polyglycine concentration is about 丨wt%, and the above-mentioned ki-R7A (manufactured by Shimadzu Corporation) is used. The diluent and the opening agent were measured by the GPC method, and the weight average molecular weight was converted by polystyrene. In addition, the tube (--) was measured using GF-7HQ (manufactured by Showa Denko Co., Ltd.) at a temperature of 5 ° C and a flow rate of 0.6 mL/min. , [Comparative Examples 2 and 3] ^ As shown in Table 1, except for the modification of tetracarboxylic oxime, Synthesis Example 1, respectively, to obtain polylysine PA2. Seiko 2 and poly-proline PA3 [Synthesis Example 4] 0.438 g of a compound ^ ^ 1.796 g of compound (W - 2) was added to a 100 mL four-necked flask equipped with a thermometer, a stirrer, and a raw material. 〇88 j 口 物 (V-1), ke g compound (V-13) and 90 200815878 25623pif 54·0 g dehydrated NMP, and dissolved under a dry nitrogen stream. Next, 0.633 g of the compound (16), 0.563 g of the compound (7), 1.686 g of the compound (1), and 15.0 g of the dehydrated BL were added, and the reaction was carried out at room temperature for 3 〇••..... .... ............., ........ ·* * · -. - . - - - - ......... *,, ·.·, Time. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to be less than or equal to 70 ° C to carry out the reaction. To the obtained solution, 25.0 g of BC was added to obtain a polyglycine solution having a concentration of 6 wt%. This polyaminic acid was designated as PA4. PA4 has a weight average molecular weight of 44,000. [Synthesis Examples 5 and 6] As shown in Table 1, a solution of polyperuric acid PA5 and a solution of polyglycine PA6 were obtained according to Synthesis Example 4 except that the tetracarboxylic dianhydride and the diamine were changed. &lt;Table 1&gt; Synthesis Example Polyproline Acid No. Tetrasine dianhydride monoamine Weight average molecular weight Compound No./slight number Moer fraction Compound number Molar fraction 1 PA1 (1) 0.5 (M-2- 1) 0.5 27,000 2 PA2 (7) (16) 0.3 0.2 (VBI-5-1) (V-1) 0.5 0.5 24,000 3 4 5 PA3 PA4 PA5 (1) -____ (1) (7) One ~W_ ( 1) (7) (8) 0.1 0.4 0.35 0.13 0.02 0.1 0.3 0.1 (W-2) (V-1 Plant (W-2) (V-13) — (V-1) (W-2) 0.5 —- --- 0.1 0.2 0.2 0.05 0.45 72.000 _J 44.000 55.000 6 PA6 ODPA 0.5 (VD 0.05 36,000 &lt;2) Preparation of liquid crystal display element &gt; [Example 1] Synthesized in a synthesis ratio of a reset ratio of 1/9 Concentration 6% by weight of poly 91 200815878 25623pif with aminic acid solution (PA1) ^ synthesis of the concentration of 6 wt% poly-proline solution (PA3) synthesized in the synthesis of the compound, per unit of polymer weight Add 10 wt% of the hetero-substituted nadic acid ylide imide compound, ie ΒΑΝΙ-μ. Thereafter, add a mixed solvent of _P/BC = 1/1 (weight ratio) to dilute the whole to 4 wt ° ° °, made of liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, as described below The liquid crystal display element was used as a liquid crystal display element. [Example 2] A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polycondensate having a concentration of 6 wt% synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. Amino acid solution (PA3). In the obtained mixture, 10 wt% of an alkenyl-substituted nadic acid ylidene imine compound, BANI-M, is added per unit weight of the polymer. Thereafter, - n is added The mixed solvent (weight ratio) was diluted to 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Example 3] A weight ratio of 1/9 was mixed and synthesized. The concentration of 6 wt% of poly=酉: solution ((5)) synthesized in Example 1 and the concentration of 6-sensitized 'polystyrene (PA3) synthesized in Synthesis Example 3. In the obtained mixture, 1 Gt per unit of polymer % '''''''''''''''' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' An agent was prepared by using a W agent as described below. [Scheme 4] The concentration of 6 wt% synthesized in Synthesis Example 1 was mixed at a weight ratio of 1/9. 200892878 25623pi f A solution of the amino acid solution (PA1) and a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3. To the obtained mixture t, 10 wt% of an alkenyl-substituted nadic acid ruthenium imide compound, i.e., compound (a-2), was added per unit of polymer reset. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Comparative Example 1] A polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a polyglycine solution having a concentration of 6 wt% synthesized in Synthesis Example 3 (PA3) were mixed at a weight ratio of 1/9. ). A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Example 5] In a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, 10 wt% of an alkenyl-substituted Nadickic acid subunit was added per unit of polymer weight. An amine compound, that is, a compound (a-i). Thereafter, a mixed solvent of NMP/BC = l/; i (weight ratio) was added, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as described below. [Example 6] In a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, 2% by weight of the compound (a-1) was added per unit weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and 93 200815878 25623pif was diluted to 4 Wt% as a whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Example 7] In a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, 10 wt% of the compound (a-1) was added per unit weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4 wt / 〇 to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Example 8] In a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, 20 wt% of the compound (a-1) was added per unit weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Comparative Example 2] ' A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA4') having a concentration of 6 wt% synthesized in Synthesis Example 4, and the whole was diluted to 4 wt. %, made into a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Comparative Example 3] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, and the whole was diluted to 4 wt%. A liquid crystal alignment agent is prepared. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. 94 200815878 25623pif [Comparative Example 4] oJ) Polyglycine solution with a concentration of 6 wt% in combination / 3). Adding 20 wt% of the compound (a, L =, NTC = 1/1 (weight ratio) of 4 wt% of the weight of the A-mother early polymer to prepare a liquid crystal alignment agent. Using the obtained fluorene alignment agent, A liquid crystal display element was produced as follows. &gt;&lt;Methods of Producing Liquid Crystal Display Element (Examples 1 to 4, Comparative Example!) A liquid crystal alignment agent was applied to a glass of two IT electrodes by a spinner (spili) The beauty cup, which has a film of fe厗70 nm formed on each soil plate.

After C was dried for 5 minutes, it was subjected to 4Q minutes at 22 Gt, and ▲ a liquid crystal alignment film was formed. Next, the night film formed on the glass substrate was ultrasonically washed in an ultrapure water towel for 5 minutes, and then dried in an oven towel for 30 minutes. L Spread 4 μm of gap material on one of the glass substrates, set the liquid crystal alignment film surface to the inside, and arrange the opposite direction in the rubbing direction anti-parallel to seal with epoxy hardener. , making a drop, 4 μιη anti-parallel unit (antiparauei cejj). In this unit, a liquid crystal composition shown below was introduced, and the injection port was sealed with a light hardener. Next, heat treatment was performed at 110 C for 30 minutes to prepare a liquid crystal display element. 95 200815878 25623pif C3H7

O - ch3 C5H11

C3h7

5wt. % 7wt. % 8wt %. 8wt. % 14wt. % 14wt. % 10wt. % 10wt. % 12wt. % 12wt. % 96 200815878 25623pif

5wt. % 7wt. % 8wt. % 8wt. % 14wt. % 14wt. %

10wt. % 10wt. %

12wt. %

12 wt. % &lt;Production method of liquid crystal display element (Examples 5 to 8 and Comparative Examples 2 to 4) &gt; A liquid crystal alignment agent was applied to two glass substrates with ITO electrodes by a spinner to form a film thickness 70 nm film. After coating, the film was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 230 ° C for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the alignment film was formed was subjected to a rubbing treatment by a rubbing device to carry out an alignment treatment. Thereafter, the alignment film was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. 97 200815878 25623pif Disperse 7 μm of gap material on one of the glass substrates, set the surface on which the liquid crystal alignment film is formed to the inside, and arrange the opposite direction in the rubbing direction, and then seal with epoxy hardener to make a gap. 7 μπι的反平.................* .. -· · ·· ~ *· - · · - ·» - - - · - - ··· · · · · ......··... * · Line unit. The liquid crystal composition shown below was injected into this unit, and the injection port was sealed with a photohardener. Then, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element.

17wt. % 17wt. %

16wt. % 10wt. % 5wt. %

10wt. %

F

6wt. % 6wt. %

13 wt. % &lt;3. Evaluation of electrical characteristics&gt; 98 200815878 25623pif For the liquid crystal display elements produced in Examples 1 to 8 and Comparative Examples 丨 to 4, the voltage holding ratio measurement and the long-term reliability measurement were performed as follows. 1) Measurement of voltage holding ratio <Test Examples 1 to 12> The voltage holding ratio measurement was carried out using a liquid crystal physical property evaluation device 6254 manufactured by Toyo Tekunika Co., Ltd. The measurement conditions are: gate width 6 〇哗, frequency 〇·3 Hz, wave height 5 v, 刿定, ,^冰

. It can be said that the greater the electrical characteristics, the better. The results are shown; 2) Measurement of long-term reliability. Test examples 1 to 5 (Examples 1 to 4 and Comparative Example υ &gt; Evaluation of retention characteristic voltage _ component for the produced liquid viscosity - ^ &gt; rate In the temperature IGGt: the method of rape 1 is to display the liquid crystal display, the voltage retention rate is measured = 100 hours, and the transit time rate is under the above conditions. Place: = 7 to: the lower the surface retention ratio (for example, The decrease in the rate is less than 曰 is greater than or equal to 10 (H, when the voltage is served &lt; Table 2 &gt;). The long-term reliability is better. The results are shown in Table, 2'.

99 200815878 25623pif For the liquid crystal produced, the rate is evaluated. The component is guaranteed to be voltage-dependent at a temperature of 60. . In the environment:;: The method is to display the liquid crystal, and the measurement of the voltage holding rate is determined under the above conditions, and the retention rate is lower when placed (for example, n夂曰f, 540 hours, if the voltage retention rate) The drop is small ^1%) The longer the reliability is, the better. The results are shown in Table 3. <Table 3>

/ 2 Tables 2 and 3, the liquid crystal alignment element using the liquid crystal alignment agent of the present invention has a voltage holding ratio of south, and the deterioration of storage characteristics can be remarkably suppressed. Yang Ding! = Fan: The month f Γ 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳 佳Therefore, the date of this issue = the scope is subject to the definition of the patent application scope attached. [Simple description of the diagram] None. [Main component symbol description] No 0 100

Claims (1)

200815878 25623pif X. Patent Application Range: 1. A liquid crystal alignment agent which is selected from the group consisting of an alkenyl substituted nadic acid ylide compound, a poly-proline and a poly-proline derivative... .... —......... .... '-..... .... .............. . . - · ' &quot; Polymer a composition of a component and a solvent, wherein the polymer component is at least one of a polymer obtained by reacting a tetracarboxylic acid dianhydride with a diamine, and the tetracarboxylic dianhydride is a compound represented by the formula (1) to the formula (17). At least one of the proportions of the polymer component based on the total amount of the composition is from 0.5 wt% to 30 wt%, and the ratio of the alkenyl substituted nadic acid ruthenium imide compound to the weight ratio of the polymer component Counted as 0.01~2, 101 200815878 25623pif Ο Ο 〇 〇 Ph 一 °&quot;:Si—0— &gt;Si^〇7Si: Ph\ /Ph .Si—0—Si^. Me phw« V .St-〇^Si^Ph 〆 , Ph (16) C (17) 2. The liquid crystal alignment agent according to claim 1, which comprises an alkenyl substituted nadic acid ylide imine compound and a derivative of polyphosphoric acid and 102 200815878 25623pif aminic acid The composition of the selected polymer component, the polymer it is a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine, the tetracarboxylic oxime oxime anhydride is a compound represented by the formula 06) and the formula (17) A mixture of at least one of the compounds shown or at least one of the compound of the formula 06) and at least one of the compounds of the formula (17) and at least one of the compounds of the formula (1) to the formula (15). The liquid crystal aligning agent according to claim 1, wherein the alkenyl substituted yttrium ylide compound is a compound represented by the formula (a), Wherein R1 and R2 are independently hydrogen, an alkyl group having a carbon number, 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, and η is 1 or 2, η Is an alkyl group having an inverse number of 1 to κ, a cycloalkyl group having a carbon number of 4, an aryl group having a carbon number of 6 to 1:2, a benzyl group, _L]_(〇)q_(L2〇^ (L1 and L2 are independently an alkylene group having a carbon number of 2 to 6, and R4 is a thiol group having a carbon number of 1-6 or 1 or 1, and "an integer of 丨~3〇", _([3) ^2_] α3 is a mercapto group having a carbon number of 1 to 4, s is 0 or 】, # is any phenylene group which may be substituted by 2_〇η, and R5 is an alkyl group having a carbon number of i4. Or -Β-Τ-Β (B is any phenylene substituted by _〇Ή, butyl) -CH2-, -C(CH3)2-, -CO-, -〇-, _s- or _S 〇2_, and β1 is a phenyl group in which the hydrogen may be replaced by -OH, and '103 200815878 25623pif is an It's an alkylene group having a carbon number of 2 to 20 and a carbon number of 5 R f and L 2 and, as a filament with a carbon number of 2 to 6, q is 0 or 1, ·, and: 2 is 1 to 3. Integer), _(l3)s_b2_l5_ (L3 and [5 is ^ 石 为 1 1 1 1 1 1 1 1 1 1 , , , , , , 1 1 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 (B2 is independently a phenylene group in which hydrogen can be replaced by Detect, and T is -sucking, -C(CH3)2_, _〇), -〇_, each or -S02·), or _B2_(10)2_c(CH3) 2_b2_〇_b2_ (β2 is independently a substitutable group in which any hydrogen can be replaced by -0Η). 4. The liquid crystal alignment agent according to claim 1, wherein the alkenyl substituted nadidonic acid imide compound is at least one of the compounds represented by the formula (a-1) to the formula (a-3). , (a-1) N-CH2 CH2 a K (a-2) The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the diamine is selected from the non-sides selected from the formula (I) to the formula (W). At least one of the chain diamine groups, f H2N-A1-NH2 (I) Wherein A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and A3 is independently a single bond, _〇, -CO-, -CONH-, _ΝΗ 〒0 ... C(CH3)2~C(CF3)2-, -0-A2-O, each m〇r, 6·1, as described in the items ii to 4 of the patent application scope, 1 06 1 , -SA -S... or a linear alkylene group having a carbon number; any hydrogen of the cyclohexane ring and the benzene ring may be fluorine, _CH3, _〇H, _c〇〇H, _s POA, a benzyl group or Hydroxybenzyl substituted 3 is a group of at least one of the non-side chain type diamines represented by 200820088878 25623pif (YU-2), (iv-i) (IV-2) (IV-15) (IV-16) (V-10) (V-11) The liquid crystal alignment agent of any one of Claims 1 to 4 wherein the diamine is selected from the non-sides selected from the formula (I) to the formula (YU). a mixture of at least one of a chain type one group and at least one of a side chain type diamine having a side chain group, the side chain group being an alkyl group having a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, An alkoxyalkyl group having a carbon number of 3 or more, a group having a steroid skeleton, and a group having a carbon number of 3 or more at the terminal, an alkoxy group having a carbon number of 3 or more, or an alkoxy group having a carbon number of 3 or more A group selected from the group of an alkyl group, HgN - A]-NH2 /1\ Wherein A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and A3 is independently a single bond, -〇, -CO-, -CONH-, - NHCO-, -C(CH3)2-, -C(CF3)2-, -0_A2-0., -S~S_S-, _S02-, -S-A2-S-, or a carbon number of 1 to 12 Linear alkylene; cyclohexane ring and 107 200815878 Any hydrogen of the benzene ring may be substituted by fluorine, -CH3, -OH, -COOH, -S03H, P03H2, benzyl or hydroxybenzyl. 8. The liquid crystal alignment agent according to claim 7, wherein the side chain type diamine is a diamine selected from the group consisting of a compound of the formula (M) and the formula (M), R7 I R6 (wherein R6 is a single bond, -〇-, face CO-, -COO-, -OCO-, -CONH-, -CH2O-, -CF2O-, or a sub-base of 1 to 6 charcoal number, Any -CH2- in the alkylene group may be substituted by -0-, -CH=CH- or -CeC-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a carbon number of 3~ An alkyl group of 30 or a phenyl group having a carbon number of 3 to 30 as a substituent, or a group represented by the formula (D-1), and any -CH2- of the alkyl group may be -0_, _CH = CH- or -C three C-substitution, Wherein R18, R19 and R20 are independently a single bond, _0-, -COO-, _OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, an oxyalkylene group having 1 to 3 carbon atoms, or An alkyleneoxy group having a carbon number of 1 to 3; a ring B and a ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; R21 and R22 are independently a fluorine or a fluorenyl group, and m and m2 are independently 0, 1 or 2; e, f and g independent 108 200815878 25623pif Fluoride group or formula is an integer of 0 to 3, the total of e, f and g is greater than or equal to i; the number of calories of 3 to 30, the alkoxy group having a carbon number of 3 to 30, and the hydrogen may be fluorine. Substituted, and any -CH2- may be substituted by a group represented by di(D-2) to a decyloxyalkyl group, an alkoxy group and an alkoxyalkyl group, R24I-Si-I R25 R26 I -O-Si— R27 7n (D-2) Burning base or carbon number 1~10 (ιχ) The number after the 1 to 30 is independently a single bond, / wherein 'R8 is independently hydrogen or a fluorenyl group; R9 is a hydrogen group, or a carbon number of 2 to 30; and, female] 〇- C0- or -CH2-) (X) a carbon number of 1 to 30 109 200815878 25623 pif -ten of an alkyl group, or an alkenyl group having a carbon number of 2 to 3 fluorene; R1〇 independently or -CH2-'· and, R&quot; and Rl2 are independently hydrogen numbers, -C:-alkyl, or phenyl) double horse 1~30 (XI) -CH-H^o'-R13 is an alkyl group having a carbon number of 3 to 30, and the number of arbitrary rock family 2 of the alkyl group is 1 6_&gt; J/CH=CH- or C〇 generation; R] 4 is independently -0 or the number is == silk; ring A4M_phenylene or cyclohexylene, 0 or l; b is 0, bt2; and, c is independent of 04!) - R17- • NH, Η2Ν^=\ ( \ R15 / one (ΧΠ) d of fluorine iJ:: two 5: an alkyl group having a carbon number of 3 to 3 fluorene or a carbon number of 3 to 3 〇 3 〇 ϋ ϋ ^ The wind or carbon number is 1 to 3 Torr, or the carbon number is 1 to alumina, and is independently -〇 or an alkylene group having a carbon number of 1 to 6; and d is independently ruthenium or osmium). ^ 9^t The liquid crystal alignment agent 3 according to item 7 of the patent scope is a diamine selected from the group consisting of compounds of the formulas (2), 4), and (M-6). 110 200815878 H2n h2n (Vlll-2) h2n 0 〇-r29 '... ' -V , h2n \ h2n (Vlll-5) r H2N (Vili-β) In the age of ί, R2S and R are independently 3 to 30 for charcoal A burnt group or an alkoxy group having a carbon number of 3 to 3 Å. 〇· As stated in the patent scope of claim 7, the liquid crystal alignment agent, 1 medium and non-chain, diamine is selected from the group consisting of formula (n), formula (IV-2), and == two formula (V4~ formula (V) -13) and the formula (IV) 2), the diamine of the group group, and the side chain type diamine is selected from the group (the group of the compound of the week, the formula (5) and the formula-6). 111 200815878 25623pif (V-12) (V-13) (VII-2) 112 200815878 25623pif Here, R28 and R29 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. The liquid crystal alignment agent according to claim 1, wherein the polymer component is at least two selected from the group consisting of at least two of the compounds represented by formula (1) to formula (17). Polylysine or a derivative thereof, tetracarboxylic acid II obtained by reacting at least one selected from the group consisting of a group of non-side chain type diamines represented by formula (I) to formula (VH) a poly-proline or a derivative thereof obtained by reacting at least one of a group selected from the group consisting of a side chain type diamine represented by the formula (M) to the formula (M), and a tetracarboxylic dianhydride and the above non-side chain A mixture of a diamine and a side k-diamine reacted to obtain a poly-anthracene acid or a derivative thereof, 113 200815878 25623pif 114 200815878 25623pif (wherein Ph represents phenyl, Me represents methyl; polymer component is a mixture of at least two polymers) '' h2n-a1-nh2 \ (V) (VI), (VII), (wherein A is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and a3 is independently a single bond, _〇 _, _c〇_, (7) cis...NHC0_, _C(CH3)2_, _C(CF3)2...〇_a2_〇..., Μ-, ·δ〇2·, -S_A2_S_, or carbon number 〖~12 A straight-chain alkylene group; any hydrogen of a hexanose and a benzene ring may be substituted by fluorine, -, 115, 200815878 25623pif -CO〇H, -S03H, P03H2, benzyl or hydroxybenzyl) R7 I R6 (wherein R6 is a single bond, -O...CO...COO-, -OCO-, -C〇NH-, -CH20-, -CF20-, or a mercapto group having a carbon number of 1 to 6, in an alkylene group Any _CH2- may be substituted by -〇-, -CH=CH- or -C tri-C-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a carbon number of 3 to 30. a phenyl group having an alkyl group or a carbon number of 3 to 30 as a substituent or a group represented by the formula (D-1), and any -CH2- of the alkyl group may be -〇-, _CH = CH -or-CeC·, Wherein R]8, R19 and R20 are independently a single bond, -0_, -COO-, "-OCO-, -CONH-, a sub-hospital having a carbon number of 1 to 4, and a carbon number of 1 to 3; Oxyalkylene, or alkyleneoxy having 1 to 3 carbon atoms; Ring B and Ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R21 and R22 are independently fluorine or A The base, ml and m2 are independently 0, 1 or 2; e, f and g are independently an integer of 0 to 3, and the total of e, f and g is greater than or equal to 1; R23 is an alkyl group having 3 to 30 carbon atoms, carbon Any of alkoxy groups having a number of from 3 to 30, or a methoxy group of a decyl group, a thiol group, and an alkoxy group having a carbon number of from 3 to 30, any hydrogen may be substituted by fluorine, and any -CH2 - may be substituted by a difluoromethylene group or a group of the formula 116 (^2) 200815878 25623pif D-2), R24 / R26 -Si -~h-0-Si - R25 ... X R27 wherein R24, R25, R26 and R27 are independently a carbon alkyl group or a phenyl group, and n is an integer of 1 to 100. The number of R〇9 is 1〇. 0-R10 (IX), NH 2 (where 'R8 is independently hydrogen or methyl; hydrogen, a base, or a dilute having a carbon number of 2 to 30; and, -CO- or -CH2-) carbon The number is i. The bracelet is a single button, 30 h2n 12 &lt;1r11A_o_r10^ (X) R12 (wherein R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group of hydrazine, or an alkenyl group having a carbon number of 2 to 3 Å; and R1G is independently 1 to 3 Å or -CHr And, Rn and independently hydrogen, nitron = 鏠, alkyl, or stupid) Humanity is 1 to 30 of 117 (XI) 200815878 25623pif (wherein, the number of R13 faces is 3~3G, the damage can be replaced by -〇-, -〇^ or substituting; the subsynthesis of diterpene = f...; ring A is M-phenylene or M is a subring : base; a is 0 or 1; b is 〇, u2; and, "independent Friend (wherein R is a fluorinated group having 3 to 3 G fluorenyl groups and 3 to 30 fluorene groups, R 6 is hydrogen, a sulphide-like wire or a fluorinated group having a carbon number of 30; R17 Independently _〇_ or an alkylene group having a carbon number of 丨~6; and, d is independently 0 or 1). Ii 12. The liquid crystal alignment agent according to claim n, wherein the polymer component is at least two selected from the group consisting of a compound represented by the formula (16) and a formula (17). Four of at least one of the compounds shown or a mixture of at least one of the compound of the formula (16) and the compound of the formula (17) and at least one selected from the group consisting of the compounds of the formula (1) to the formula (15) The carboxylic acid dianhydride is selected from the group consisting of (W - D, formula (rv - 2), formula (IV-15), formula (IV-16), formula (v - i) - formula (v - 13) and formula ( YU-2) is a polyglycine or a derivative thereof obtained by reacting at least one of a group of non-side chain type diamines represented by a tetrabasic acid dianhydride and a selected one (formula 2) Ships 4), (Shan~5) and (5)-6) 118 200815878 25623pif Polyamide or its derivatives obtained by at least one reaction of a group of side chain diamines, and by four Polylysine or a derivative thereof obtained by reacting a carboxylic acid dianhydride with a mixture of the above-mentioned non-side chain type diamine and a side chain type diamine, \ 119 200815878 256 23pif (V-12) (V-13) (VII-2) 120 200815878 25623pif (Vi 11-5) (VIII-6) wherein R28 and R29 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. A liquid crystal alignment film obtained by firing a liquid crystal alignment agent according to any one of claims 1 to 12 in a film state. A liquid crystal display device comprising: a pair of substrates disposed oppositely; an electrode formed on one or both of surfaces facing each of the pair of substrates; and a surface formed on each of the pair of substrates facing each other A liquid crystal alignment film according to claim 13; and a liquid crystal layer formed between the pair of substrates. 121 200815878 25623pif VII. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the 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: 6