TW200831611A - Liquid crystal aligning agent and liquid crystal displays made by using the same - Google Patents

Abstract

The invention provides a liquid crystal alignment layer which has a high voltage holding ratio and permits speedy relaxation of a residual charge accumulated by the application of DC voltage even after long-time exposure to high temperature. A liquid crystal aligning agent containing the following components (A) and (B): (A) a polymer which is obtained by subjecting a polyamic acid composed of repeating units represented by the structural formula [1] to imidation and which contains 0.1 to 3 carboxyl groups per repeating unit on the average: [1] (wherein R1 is a tetravalent organic group; R2 is a divalent organic group; and n is a positive integer) and (B) an amine compound having one primary amino group and a nitrogenous aromatic heterocycle in the molecule in which the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Description

[Technical Field] The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] At present, a liquid crystal alignment film of a liquid crystal display element mainly uses a liquid crystal alignment treatment agent (also referred to as liquid crystal) which is a solution of a polyamidene precursor such as polyacrylamide or a solution of soluble polyimine. The alignment agent is applied to a glass substrate and fired, and is called a polyimide film. The liquid crystal alignment film is intended for the purpose of controlling the alignment state of the liquid crystal. However, with the refinement of the cylinder of the liquid crystal display element, it is required to control the contrast of the liquid crystal display element to reduce or reduce the afterimage phenomenon, so the order is high in the liquid crystal alignment film used therein, or the residual voltage is applied. It is important that the charge is low and/or the relaxation of the residual charge accumulated by the DC voltage is fast. In the polyimine-based liquid crystal alignment film, the time until the disappearance of the afterimage due to the DC voltage is short, and the polyamine or the ruthenium-containing polyamine is added to the specific structure. A liquid crystal alignment agent containing a soluble polyimine (for example, refer to Patent Document 1) or a liquid crystal alignment agent containing a soluble polyimine which is used as a raw material for a specific diamine such as a pyridine structure (for example, refer to Patent Document 2) ), etc., is known. Further, the time when the voltage holding ratio is high and the afterimage until the disappearance of the afterimage due to the direct current voltage disappears is based on the use of a small amount of -6 - 200831611 except for polyacrylic acid or its ruthenium iodide polymer. a liquid crystal alignment agent selected from the group consisting of a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing i tertiary amino groups in the molecule (for example, see Patent Document 3). The system is known. However, in recent years, large-screen, high-definition liquid crystal televisions have been widely used. The liquid crystal display elements of this type are more demanding for afterimages than the display devices that have been mainly displayed by characters or still pictures. Durable for long-term use in harsh environments. Therefore, the liquid crystal alignment film used therein must have higher reliability than the conventional one. Regarding the electrical characteristics of the liquid crystal alignment film, not only the initial characteristics are required to be good, but also good characteristics can be maintained, for example, after prolonged exposure at a high temperature. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. For those who have the above situation. In other words, the problem to be solved by the present invention is to provide a liquid crystal alignment treatment of a liquid crystal alignment film which has a high voltage holding ratio and can be quickly neutralized by a residual voltage accumulated by a DC voltage even after exposure for a long time at a high temperature. Agent. Further, it is possible to provide a liquid crystal display element which can withstand long-term use and has high reliability in a severe use environment. In order to solve the above problems, the inventors of the present invention have found that the liquid crystal 200831611 alignment treatment agent containing a specific polyimine and a specific amine compound is more specifically mixed in an organic solvent. The liquid crystal alignment treatment agent obtained by polyimine and a specific amine compound can solve the above problems, and the present invention has been completed. In other words, the present invention has the following features as the gist. (1) A liquid crystal alignment treatment agent comprising the following (A) component and (B) component, (A) component: a polyimine having a carboxyl group in a molecule, and (B) a component: having a molecule One primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the primary amine group is bonded to an aliphatic hydrocarbon group or an amine compound of a non-aromatic cyclic hydrocarbon group. (2) The liquid crystal alignment treatment agent according to (1), wherein the component (A) is a polymerization in which the polyamic acid formed by the structural formula of the repeating unit represented by the following formula [1] is imidized. The amount of carboxyl groups of the polymer is 〇·1~3 '[1] for the repeating unit of the polymer.

[1] (In the formula, Ri is a tetravalent organic group, and R2 is a divalent organic group 'β is a positive integer). (3) The liquid crystal alignment treatment agent according to (1), wherein the (Α) component is such that a part or all of the repeating unit in the structural formula of the repeating unit represented by the formula [1] has the following formula [2] 〕The structure of the unit shown-8-

200831611 The amount of polymer obtained by polyamidolic acid is imidized. The average amount of the repeating unit of the polymer is 化2.

(wherein R3 is a tetravalent organic group, and R4 is at least one of r4 having a carboxyl group). (4) The agent according to any one of (1) to (3) wherein the component (B) is a compound of the following formula [3], and the carboxyl group of the polymer is 1 to 3, [2] a divalent organic group, R3 or a liquid crystal alignment treatment of the amine compound, h2n

[3]

(wherein 'X! is an aliphatic hydrocarbon group or a non-valent organic group, and χ2 is a nitrogen-containing aromatic heterocyclic ring) (5) as in any one of (1) to (4)' The component B) is represented by the following formula [4]: h2n (wherein X3 is an aliphatic or hydrocarbon group having a carbon number of 1 to 1 ,, and X4 is a single bond, -〇-, -NH-, - S-, a divalent organic group, and a carbon 1 of an anthracene 3 and an anthracene 4; an amine compound represented by a liquid crystal alignment treatment of an aromatic cyclic hydrocarbon group, [4] : a basal, non-aromatic ring type; 2 - or a carbon number of 1 to 19 (the total amount of the sub-components is 1 to -9-200831611 20, and X5 is a nitrogen-containing aromatic heterocyclic ring which may have a substituent). (6) Liquid crystal alignment as described in (5) The treatment agent, wherein the component (B) is an amine compound selected from the group consisting of X3, X4 and X5 of the formula [4], each selected from the group or ring combination described below, wherein the X3 system is one selected from the group consisting of carbon number 1. a straight or branched alkyl group having 1 to 10 Å, an unsaturated alkyl group having 1 to 1 carbon number, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane Alkane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, ring twelve Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, cyclohexadecane ring, a group consisting of a tricyclohexadecane ring, a tricyclotetracosane ring, a bicyclo Gentane ring, a decahydronaphthalene ring, a raw spinane ring, and an adamantane ring; the X4 system is one selected from the group consisting of a single bond, -〇-, -NH-, -S-, -S02-, SX, -CO-0-, -〇-CO-, -CO-NH-, -NH-CO-, -CO with carbon numbers 1 to 19 -, -CF2-, -C (CF3) 2-, -CH(OH)-, -C(CH3)2-, -Si(CH3)2-, -Ο-Si(CH3)2-, -Si ( CH3) 2-〇-, -Ο-Si(CH3) 2-0-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, ring 壬An alkane ring, a cyclodecane ring, a cycloundecyl ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, Cyclooctadecane ring, cyclohexadecane ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinel ring, diamond Alkane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, ring ring, ring Anthracycline, anthracene ring, phenanthrene ring, phenanene ring, pyrrole ring, oxime ring, oxime ring, thia π ring, b υ 2008 200831611 ring, pyridine ring, pyrimidine ring, quinoline ring, Pyrazoline ring, azole ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring triazole ring, pyrazine ring, benzimidazole ring, m-diazepine phenanthroline ring, anthracene ring, a group of quinoxaline ring, benzothiazole ring oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine and morpholine ring, or a combination of several combinations; X5 is one type Selected from pyrrole ring, imidazole ring, spiro π ring, ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, azole ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline pyrazole Alkane ring, triazole ring, pyrazine ring, benzimidazole ring, Emperor I& Lin 哀, non-circular ring, 卩 卩 ring, quinoxaline D ring, phenothiazine ring, oxadiazole ring, Acridine rings, and groups of such substituents. (7) The agent according to any one of (1) to (6), which is contained in a ratio of 0. 01 to 2 moles per 1 mole of the poly(imine) component (A). (B) The agent according to any one of (1) to (7) wherein the poly(imine) of the (Α) component is heated and mixed or mixed in an organic solvent. (9) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above. (10) A liquid crystal display element characterized by a liquid crystal alignment film. Isoquinoline ring, anthracene, pyrazolidine ring, tinoline ring, phenothiazine ring, ring, dioxin ring thiazole ring, pyrazole isoquinoline ring, anthracene ring, triazine ring, two The nitrogen oxime ring, the benzothiazole ring, and any one may have a carboxyl group contained in the liquid crystal alignment treatment. Liquid crystal alignment treatment Amine compound is obtained by heating (1) to (8) I is as shown in (9) -11 - 200831611 [Effect of the invention] The liquid crystal alignment treatment agent of the present invention can be obtained by a relatively simple method. Further, the liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio and can obtain a liquid crystal alignment film which is rapidly neutralized by a residual charge accumulated by a direct current voltage after being exposed for a long time at a high temperature. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. [Best Mode for Carrying Out the Invention] The liquid crystal alignment treatment agent of the present invention contains (A) a component: a polyimine having a carboxyl group in a molecule (hereinafter also referred to as a specific polyimine), and (B) a component: an amine compound having one primary amino group (-NH2) and a nitrogen-containing aromatic heterocyclic ring in a molecule, and the primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group (hereinafter also referred to as A liquid crystal alignment treatment agent which is a specific amine compound). More specifically, it is a liquid crystal alignment treatment agent obtained by mixing a specific polyimine of the component (A) and a specific amine compound of the component (B) in an organic solvent. In the present specification, the above-mentioned amine group (-NH2) is synonymous with a first-order amine group, and is hereinafter also referred to as a first-order amine group. In the liquid crystal alignment treatment agent of the present invention, it is considered that a first-stage amine group in a specific amine compound forms a salt with a carboxyl group in a specific polyimine, or a carboxyl group or a carboxyl group in a specific polyimine. With the detachment of water or alcohol, the indoleamine bond, or the ruthenium imine group in a specific polyimine, with -12-200831611 when the ring of the quinone imine group is opened and the reverse film is bonded Depending on the firing process, it is conceivable to form a first-order amine group of the salt, and the water is removed from the liquid crystal alignment treatment agent of the invention, and regardless of the presence, it is possible to effectively bond the liquid crystal with the specific polyimine. The reason. Further, the specific amine compound contains nitrogen and its conjugated structure has a charge shift in the electron-beating lateral film. Further, when the aromatic heterocyclic ring is bonded to the electrostatic interaction of the knot in the specific polyimine, the group acts on the nitrogen-containing aromatic group in the specific amine compound. In addition, the specific amine compound is chemically bonded, so that the nitrogen-containing aromatic can effectively make the polyimine molecule intramolecularly and minutely. According to the above, the liquid crystal to the film of the present invention can be considered to be DC voltage. It is used quickly and has long properties even at high temperatures. <(A) Component/Specific Polyimine] In the present invention, a polyimine having a carboxyl group in the molecule of the component (A) can be produced. The polyimine is treated with tetracarboxylic dianhydride. Further, the liquid crystal is prepared by mixing a carboxyl group in a specific polyimine to form a guanamine bond. As a result, a simple method of mixing in the solvent of the organic solvent, the specific amine compound and the aromatic heterocyclic ring, by virtue of the function, can promote the formation of a salt or a salt by a carboxyl group containing nitrogen when the liquid crystal is aligned with the liquid crystal alignment film. Hydrogen bonding causes a charge shift between the caro-aromatic heterocycles in a particular polyimine, due to the charge that moves with the particular polyamidene into the heterocyclic moiety, and moves between the sub-substituents. The relaxation of the residual charge of the liquid crystal distribution accumulated by the alignment treatment agent can maintain the specific polyimine after time exposure, as long as it is not particularly limited in its structure and the diamine is relatively easy to obtain -13- For the reason of 200831611, a polymer obtained by imidating a polyamino acid formed by a structural formula of a repeating unit represented by the following formula [1] is preferred. 〔化5〕

Positive integer). Further, in the formula [1], Ri and R2 may be of the same type, or may have different types of Ri and R2, and a plurality of different types may be combined as a repeating unit. The specific polyimine is usually produced by controlling the imidization ratio of the above polyamino acid to less than 100% when the imidization is carried out. Further, the specific polyimine can be obtained by subjecting a polyamino acid having a structural unit represented by the following formula [2] to a repeating unit in a structural formula of a repeating unit represented by the formula [1]. Made. [6]

(wherein R3 is a tetravalent organic group, r4 is a divalent organic group, and at least one of r3 or r4 has a carboxyl group). -14- 200831611 At this time, the sulfhydrylation rate can also be 100%. The imidization ratio of the specific polyimine is preferably 20% or more, more preferably 40% or more, on the basis of a high voltage holding ratio. The amount of the carboxyl group in the specific polyimine (the average enthalpy in the repeating unit of the structural formula of the polyimine) is more effective in obtaining the effect of the present invention, and the structure as the polyimine The average repeating unit is preferably 0.1 to 3, more preferably 3 to 2.0, and the most preferred is φ 5 5 to 1 · 8. The repeating unit at this time may also be a unit combining an amino acid group which is not imidized by hydrazine. For example, in the case of a polyimine obtained by imidating a polyamic acid formed by a repeating unit represented by the formula [1], when the ruthenium imidization ratio is less than 100%, the following may be considered. The structural unit of the formula [5a] to [5d] constitutes a repeating unit of the amount of the thiol group obtained as described above, and includes all of the formulas [5a] to [5d].

In the present invention, the amount of the carboxyl group in the specific polyimine (also referred to as the average enthalpy of the sum of the carboxyl group and the Q of (Η)) is obtained by the following (i) p, -15-200831611. (i) For the repeating unit derived from the carboxyl group of the amino acid which is not imidized, and the structural formula of the polyimine, the average 値: p (ii ) is in the R3 and R4 of the above formula [2]. The average carboxyl group of the carboxyl group and the repeating unit of the structural formula of polyimine: Qo. Next, the P′ of (i) above can be used for the imidization ratio (z), and the following formula (1) can be used. take. Further, the ruthenium amination ratio (z) can be obtained, for example, from the measurement of <醯imination rate > P=2X (lz/100) (Formula 1) The Q of the above (ii) is a repeating unit of a structural formula represented by R3 in the above formula [2] and a structural formula of polyimine. The sum of the average 値Q!, the carboxyl group contained in R4, and the average 値Q2 as a repeating unit of the structural formula of the polyimine. Each of R3 and R4 described above is a part or all of a tetracarboxylic dianhydride residue (R3) and a diamine residue (R4) which are used as a raw material for producing a specific polyimine.

Therefore, the above is the molar fraction of the tetracarboxylic dianhydride represented by the following formula [V 1] in the total molar amount of the tetracarboxylic dianhydride used in the production of the specific polyimine. It is obtained by the following formula (3). [Chemical 8] Ο 0

- 16- 200831611 Q = j3 XW /W (Formula 3) 1112 wherein β: represents the number of carboxyl groups contained in R3, and Wi is the molar amount of tetracarboxylic dianhydride of formula [VI], w2 It represents the total molar amount of tetracarboxylic dianhydride. In addition, in the above-mentioned Q2, the molar fraction of the diamine represented by the following formula [V2] in the total molar amount of the diamine used in the production of the specific polyimine is used, and the following formula (4) Seek. [9] h2n-R4-nh2 [V2] Q=02XW/W4 Test 4) wherein β2 represents the number of carboxyl groups contained in R4, and W3 is the molar amount of the diamine of formula [V2]. W4 represents the total molar amount of diamine. The amount of such a carboxyl group is determined by the following (Formula 5). The amount of the carboxyl group in the specific quinone imine = P + Q1 + Q2 = 2X (1 - Z / 100) + \XW / W2W2XW / W4 (Formula 5) In the present invention, the amount of the carboxyl group in the specific polyimine The adjustment may be (1) a method of adjusting the yield of ruthenium iodide, (2) a number of carboxyl groups contained in R3 or R4 of the formula [2], and a complex of the formula shown in the formula [1] Any one of the methods for adjusting the ratio of the formula [2] of the unit. In addition, the methods of (1.) and (2) can also be used. With respect to the degree of freedom in selecting Ri and R2 in the formula [1], the method of (1) is preferred. The method of (2) is preferred in terms of the degree of freedom of choice of the imidization ratio of the specific polyimine. Further, in the firing process in the production of the liquid crystal alignment film -17-200831611, the oxime imidization reaction is carried out to remove the specific amine compound or to reduce the possibility that the polyimine chain is cleaved. 2) The method is preferred. When the amount of the carboxyl group in the specific polyimine is adjusted by the method of the above (1), I and h of the formula [1] are not particularly limited. Further, R1 and R2 may be the same type in the formula [1], or may have different types of R1 and R2' and may be combined into several different types as repeating units.

The specific example of R1 in the formula is as follows.

— 18, 200831611 〔化1 〇〕 A-1 Α·2 h3c, ch3. A-3 h3c ch3 Α·4 h3c ch3 _____ 〆----- H3C CH3 A-5 Female A-6 A-7 Introduction A *8 XX A*9 XX A· 10 xc Α·11 ax A-12 ym A· 13 A-14 〆^ A· 15 A-16 A-17 A· 18 ch3 A· 19 Α·20 :h3 A. 21 V ch3 A*22 A-23 x>c A-24 XX: A.25 TC Α·26 XC A-27 xa A-28 SA*29 A-30 -19- 200831611 〔化11〕 Α·31 A -32 A-33 »xc Α-34 Xr°^CC A-35 A-36 xbrS〇c Α-37 A.38 FsC^CFa :03⁄4 Α·39 Α·40 ooc Α·41 OK. A-42 &gt ;m: Α·43 Α·44 CH3 ^OtC H3C A-45 CH3 h3c Α-46 ic Among these, A-6, A-16, A-18~A-22, A-25, A- 37, A-3 8 and A_46, which are polyimines having a high yield of hydrazine, are preferred because of their high solubility in organic solvents. Further, when 10% or more of 1% or more of the above has an alicyclic structure or an aliphatic structure such as A-1 to A-25 and A-46, it is preferable because the voltage holding ratio can be increased. In particular, I is preferably a liquid crystal alignment film which is selected from the group consisting of two kinds of A-1, A-16 and A-19 because it can produce a rapid relaxation of charge. A specific example of the rule 2 in the formula [1] is as follows. -20- 200831611 〔化1 2〕

Bl B-2 XX B-3 xra Β·4 XJ ΙΑ B-5 H3〇xraCH3 B*6 Β*7 B-8 众B-9 XT Β-10 〇-ch3 -ό- B-ll XCCH3 Β·12 H3c )-ch3 -0- Β-13 ch3 XX^CH3 B-14 XiC B-15 cr Β-16 B-17 B-18 Β.19 B-20 B-21 xr Β-22 B-23 ~8- B-24 8= Β-25 B-26 H3c ch3 ^0τ Β·27 ch3 h3c Β·28 PF3 ~^Sr^r F3C Factory B-29 xra B-30 xra Β·31 XrsXX B-32 B-33 - 21 - 200831611 〔化1 3〕

B-34 oV B-35 B-36 O^r Β·37 h3c ch3 /03⁄4 Β·38 f3c cf3 ira B-39 F3c cf3 Β-40 Η B*41 Β·42 Β-43 B-44 B-45 Β-46 ~QrJF^r Β·47 B.48 -Qr^Or Β·49 B-50 Β·51 iX -22 - 200831611 〔化1 4〕

Β·52 B-53 Β-54 Μ B*55 J〇r°xi〇xr Φο 0 Β-56 iTY〇Nir^ fY B-57 U lA Β-58 wxr B*59 Β60 F B-61 h3c ch3 J7 . people. XX Β·62 ch3 OgO^xr B-63 xx〇x?a〇xr Β·64 xijyb<xr B-65 众—χχα Β·66 -(CH2)n- n = 2~12 B-67 ch3 —( CH^-C-iCH^ ch3 Β-68 ch3 a (ch2)4-?-(ch2)3-ch3 Β·69 ch3 ch3 a CH2_6-(CH2)2-6 - (CH2)2— Η H Β· 70 ! ch3 ch3 - CH?- G-(CH2)2· C_ (CH^- Η H B-71 ch3 ~(CH2)2-C-(CH2)5-H -23- 200831611 [Chemical 1 5]

Β·72 ch3 —(CH^-C—(called a B-73 —(CH2)3-0-(CH2)2-0-(CH2)3- Β-74 ch3 ch3 a Si-O-Si- (ΟΗ^—ch3 ch3 B-75 -H0-(CH2)n-^Q- n = 3~12 Β-76 XrwXX n = 2~12 B-77 Ol0jCtwXX·^ n = 2~12 Β*78 η = 2~12 B-79 η = 2~12 Β-80 XT. One (CH2)nCH3 η = 5~19 B-81 XC - (CH2)nCH3 η = 5~19 Β·82 η = 0~21 B- 83 η = 0 〜21 Β-84 η = 0~21 B-85 η = 0~21 Β·86 η = 0~21 B-87 ~{ ^(CH2)nCH3 η = 0~21 Β·88 n ± r 〇~21 B-89 ^^~{ y^Q(CH2)nCH3 η = 2~19 Β·90 η = 0~21 B-91 ^~^^~0(CH2)nCH3 η = 0 〜21 Β *92 B-93 -24 - 200831611 [Chem. 1 6]

- 25- 200831611 〔化1 7〕

(In B-112 and B-113, Q system means -(:0〇-, -〇〇:0-, -(:01^-, -NHCO-, -CH2-, -0-, -CO-, Any of -NH-) In the case where part or all of R2 is B-80 to B-101, the pretilt angle of the liquid crystal can be increased. When the liquid crystal is vertically aligned, the preferred r2 is 5~ 1〇〇mol% (more preferably 1〇~8〇mole b-80~B-1〇1, etc.) The method of (2) above is used to adjust the carboxyl group in a specific polyimine. When the amount of either R3 or R4 has a carboxyl group structure, there is no particular limitation of -26 - 200831611. Moreover, the number of carboxyl groups is 〇~2 for each of R3 and R4 (only one of R3 or R4 has at least In view of the ease of synthesis of the polyimine and the availability of the raw material, it is preferred that R4 has a carboxyl group, and R4 having a carboxyl group is, for example, B-102 to B-113. When R4 is a carboxyl group, the structure of R3 is not particularly limited, and specifically, for example, A-1 to A-46. [Specific polyimine] Manufacturing method > (A) component used in the present invention The method for producing the specific polyimine is not particularly limited, and generally, one or several kinds of tetracarboxylic acid components selected from tetracarboxylic acids and derivatives thereof, and one or several kinds of diamine compounds are used. The resulting diamine component is reacted to obtain a polylysine having a structural formula of a repeating unit represented by the formula [1], and the polyamic acid is subjected to hydrazylation. φ At this time, the obtained The polyamic acid can form a monomer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component of the raw material. The tetracarboxylic acid and its derivative referred to herein, It is a tetracarboxylic acid, a tetracarboxylic acid dihalide, and a tetracarboxylic dianhydride. Among them, tetracarboxylic dianhydride is preferable because it has high reactivity with a diamine compound. Specific examples of the method for producing the amine. For example, at least one tetracarboxylic acid component selected from the group consisting of the tetracarboxylic dianhydride represented by the formula [6] and at least one selected from the group consisting of the formula [7] can be used. - 200831611 shows the diamine component of the diamine compound in N-methylpyrrolidone, n, N,-dimethyl Amides, n, n, - carry out polycondensation reaction of dimethylformamide, [gamma] -butyrolactone and the like of an organic solvent to prepare a polyamide acid of [18] Ο 0.

Further, the Ri of the formula [6] is the same as the definition of the formula [1], and the specific examples of Ri are as described in the above-mentioned A-1 to A-46. [Chem. 19] - R2 - NH2 [7] Further, the R2 of the formula [7] is the same as the definition of the formula [1], and the specific example of R2 is as described in the above-mentioned B-1 to B-1 13 Recorded. In this case, the reaction temperature may be selected from any of -2 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. The ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to the total number of moles of the diamine compound constituting the diamine component is preferably 〇8 to 1.2. When the molar ratio is close to 1.0, the degree of polymerization of the resulting polymer becomes large. Further, in the case where the partial or total repeating unit of the repeating unit of the formula [1] has a polylysine having a unit of the formula [2], a tetracarboxylic dianhydride having a carboxyl group in R1 can be used. And/or a diamine having a carboxyl group in R2. A method for the imidization of a polyamino acid is generally carried out by heating at -28 - 200831611 with ruthenium imidization, using a catalyst oxime imidization to carry out oxime imidization at a lower temperature. The method of imidization of the catalyst oxime of the reaction does not easily cause a decrease in the molecular weight of the obtained polyimine. The catalyst oxime imidization allows the polyamino acid to be carried out in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the ruthenium imidization, but if it is too high, the molecular weight of the polyimine will decrease. The amount of the alkaline catalyst is 0 · 5 to 30 moles of the valeric acid group, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles of the prolyl group. The best is 3 to 3 0 moles. When the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and when it is too large, it is not easily removed completely after completion of the reaction. The basic catalyst to be used at this time is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, acridine is preferred because it has an appropriate basicity in carrying out the reaction. Further, an acid anhydride such as acetic anhydride, trimellitic anhydride, pyromellitic anhydride or the like, wherein acetic anhydride is used, is preferred because it is easily purified after completion of the reaction. The organic solvent is not particularly limited as long as it can dissolve the polylysine, and specifically, for example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-A Base-2-pyrrolidone, N-methylcaprolactone, dimethyl submilling, tetramethyl urea, dimethylhydrazine, hexamethylarylene, γ-caprolactone, and the like. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The produced polyimine can be obtained by charging the above reaction solution into a poor solvent and recovering the resulting precipitate. The poor solvent to be used at this time is not particularly limited, and is, for example, methanol, acetone, hexane, butyl cellosolve, -29-200831611 heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water. Wait. The polyimine which has been introduced into the poor solvent through the sinking chamber can be subjected to normal temperature or heat drying under normal pressure or reduced pressure after filtration to form a powder. The polyimine is also recrystallized by repeating 2 to 1 times to re-dissolve the quinone imine powder in an organic solvent for reprecipitation. It is preferable to carry out the refining process when the impurities cannot be completely removed by a single precipitation recovery operation. The molecular weight of the specific polyimine used in the present invention is not particularly limited, and is easy to handle, and in terms of stability of properties at the time of film formation, the weight average molecular weight is preferably 2,000 to 200,000, more preferably 4,000 to 50,000. good. The molecular weight is determined by GPC (gel permeation chromatography). <(B) Component/Specific Amine Compound> The specific amine compound of the component (B) used in the present invention has one amine group (NH2) and a nitrogen-containing aromatic heterocyclic ring in the molecule, and # The amine group (the amine group 1) is bonded to an amine compound of an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. _ The specific amine compound has only one of the amine groups contained in the molecule, which can avoid the problem of polymer precipitation or gelation when preparing the liquid crystal alignment agent or during storage of the liquid crystal alignment agent. . The primary amine group contained in the specific amine compound is liable to form a salt or a bonding reaction with a specific polyamidiamine, and must be bonded to an aliphatic hydrocarbon or a non-aromatic ring containing no aromatic hydrocarbon in the molecule. On the hydrocarbon base. Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, an alkyl group having a branched structure of -30 to 200831611, a hydrocarbon group having an unsaturated bond, and the like. Preferably, the carbon number is 1 and the carbon number is preferably 1 to 15, and the carbon number is preferably 1 to 10. Specific examples of the non-aromatic cyclic hydrocarbon group, such as a cyclopropane ring, a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a ring, a cyclodecane ring, a cycloundecane ring, Cyclododecane ring, cyclotridecanetetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane cyclooctane ring, cyclopentadecane ring, cyclohexadecane ring, tricyclic ring Eicosanecyclotetracosane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinane ring, alkane ring and the like. Preferably, it is a ring formed by a carbon number of 3 to 20, more preferably a ring of 3 to 15 carbon atoms, and most preferably a cyclic ring hydrocarbon group formed by a carbon number of 3 to 10 carbon atoms. The specific nitrogen-containing aromatic heterocyclic ring contained in the compound is at least one aromatic cyclic hydrocarbon selected from the structures of the following formula [8a], formula [8b] and formula [8c], preferably 1 ~ 4 pieces.化20] 〜2 0, butane ring decane ring ring, ring, ring ten, three ring and diamond just by carbon number non-aromatic

[8b] [8c] (wherein, it is a linear or branched alkyl group having a carbon number of 丨~5) specifically s 'such as a pyrrole ring, an imidazole ring, an oxazole ring, a thipyraz ring, a pyridine ring, a pyrimidine Ring, quinoline ring, pyrazoline ring, iso, oxazolyl ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring, ring, diazole ^, pyrazine ring, benzimidazole ring, two Aziridine ring, azole ring, quinoline ring pyrazolidine lininoline-31 - 200831611 ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazine ring , acridine ring, etc. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring may have a substituent containing a hetero atom. More preferably, the specific amine compound is an amine compound represented by the following formula [3]. 〔化 2 1〕

[3] (wherein, Xi is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X2 is a nitrogen-containing aromatic heterocyclic ring). In the formula [3], X! The divalent organic group of the aliphatic hydrocarbon group or the non-aromatic ring-type nicotyl group is not particularly limited.

The preferred X! in the formula [3] is a divalent organic group having i kinds of aliphatic hydrocarbon groups selected from the group consisting of 1 to 2 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. The non-aromatic cyclic hydrocarbon group is, for example, the above configuration. More preferably, it is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a raw spinane ring, an adamantane ring, and the like. More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 1 Å. Further, -CH2- contained in any of the aliphatic or non-aromatic cyclic hydrocarbon groups adjacent to the amine group contained in X! may also be -〇-, -NH-, -CO-0-, -o- Co-, -CO-NH-, -NH-CO-, -CO-, -S-, -S ( 0) 2-, -CF2-, -C ( CF3 ) 2-, -c ( CH3 ) 2- , -32 - 200831611 -Si (CH3) 2-, -Ο-Si (CH3) 2-, _Si (CH3) 2-0_, -O · S i ( CH 3 ) 2 - 0 -, cyclic hydrocarbon group and hetero Ring replacement. Further, a hydrogen atom bonded to any carbon atom may be a linear or branched alkyl group having a carbon number of 1 to 20, a cyclic hydrocarbon group, a fluorine-containing alkyl group having a carbon number of 1 to fluorene, a heterocyclic ring or a fluorine atom. Hydroxyl substitution. Specific examples of the cyclic hydrocarbon group such as a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a molybdenum ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a phenanene ring, a ring φ propane ring, or a cyclobutane a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecyl ring, a cyclododecane ring, a cyclotridecane ring, Cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, cyclohexadecane ring, tricyclohexadecane ring, three Cyclotetradecane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinach ring, adamantane ring, and the like. Further, specific examples of the heterocyclic ring are, for example, a ring, a π ring, a π ox ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, Indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyridene ring, benzimidazole ring, m-diazepine ring, dinoline ring, non A porphyrin ring, an 11th hydrazine ring, a quinoxaline ring, a benzothiazepine ring, a phenothiazine ring, an oxadiazole ring, an acridine ring or the like. In the formula [3], the oxime 2 is a nitrogen-containing aromatic heterocyclic ring, and similarly to the above, an aromatic ring having at least one structure selected from the group consisting of the formula [8a], the formula [8b] and the formula [8c] Hydrocarbon. Specifically, for example, the configuration described above. Among these, a contiguous ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine, a diazine ring, a diazole ring, a pyrazine ring, a benzimidazole ring, and a m-diaza-33 - 200831611 Anthracycline, quinoxaline ring, azepine ring, dioxetane ring, ring, anthracene ring are preferred. Further, the easy value of the electrostatic interaction of the nitrogen-containing aromatic heterocyclic ring with a specific polyfluorene to form a salt or a hydrogen bond is not the same as the substituent of the formula [8a], the formula [8b], and the adjacent substituent contained in X2. The knot is better. Further, the nitrogen-containing aromatic heterocyclic ring of X2 of the formula [3] may have a substituent of a halogen atom and/or an organic group, and a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. The preferred combination of Χι and χ2 in the formula [3] is: a divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 3 to 2 carbon atoms, and the oxime 2 is selected from the group consisting of pyrrole rings. Ring, pyridyl D ring, pyrimidine D ring, indole ring, triazine ring, tris, benzimidazole ring, m-diazepine ring, quinoxaline ring, mouth, Guang Geng ring, naphthalene D ring, A phenazine ring, a pyridazine ring. Further, the carbon atom of the group heterocyclic ring may have a halogen atom and/or a group, and the organic group may further contain an oxygen atom, a sulfur atom or a nitrogen atom. More preferably, the specific amine compound is a compound of the formula shown below. [Chem. 22] /Χ3 /Χ5 H2N'[4] (wherein X3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group i in a naphthyridine ring or a phenazineimine, and X i and The carbon atom of the [8c] phase may also be substituted by a nitrogen-containing aromatic organic group having one non-aromatic cyclic imidazole ring, pyrazolazole ring, pyrazine cycloheptene ring and dioxane X2. Atoms such as atoms: 4) amine non-aromatic ring -34- 200831611 hydrocarbon group, X4 is a single bond, -0-, -NH-, -S-, -S〇2· or carbon number 1 The hexavalent organic group of ～19, and the total of the carbon atoms of χ3 and χ4 is 1 to 2〇, and the Χ5 is a nitrogen-containing aromatic heterocyclic ring which may have a substituent. The oxime 3 of the formula [4] is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic aromatic hydrocarbon group. Specifically, for example, a linear or branched alkyl group having 1 to 1 carbon atom, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane. Alkane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring ten Hexacyclo ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, ten Hydrogen naphthalene ring, raw spinel ring, adamantane ring, and the like. Preferred is a linear or branched alkyl group having a carbon number of 1 to 10, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, or a ring oxime. An alkane ring, a cyclodecane ring, a cycloundecyl ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a raw spinane ring, an adamantane ring. More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 1 fluorene. -CH2- contained in χ3, which is not adjacent to any of the aliphatic or non-aromatic cyclic hydrocarbon groups of the amine group, may also be -0, -11-, -(:0-0-, -O- CO-, -CO-NH-, -NH-CO-, -CO-, s-, -S (0) 2-, -CF2-, -C (CF3) 2-, -C (CH3) 2-, -Si ( ch3) 2-, •0 Lai Si (CH3) 2-, -Si (CH3) 2-0...-Ο-Si (CH3) 2-0-, a cyclic hydrocarbon group and a heterocyclic ring. a hydrogen atom bonded to any carbon atom, or a linear or branched alkyl group having a carbon number of 1 to 20, a cyclic hydrocarbon group, a fluorine-containing alkyl group having a carbon number of 1 to 10, a heterocyclic ring, a fluorine atom, or a hydroxy group. The -35-200831611 cyclic hydrocarbon group and heterocyclic ring referred to herein are synonymous with those described in the formula [1]. The X4 system of the formula [4] is a single bond, 〇-, -NH-, -S -, -S02- or a divalent organic group having a hindrance of 1 to 19. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may also contain An oxygen atom, a nitrogen atom, a sulfur atom, a ruthenium atom, etc. The specificity of the X4 is as follows. For example, a single bond, -0-, -NH-, -S-, -S02- or a carbon number of 1 to 19 , -CO-O-, -0-C0-, -CO-NH-, -NH-CO- , -CO-, -cp], -C(CF3) 2-, -CH(OH) -, -C(CH3) 2-, -Si(CH3) 2-, -〇-Si (CH3) 2-, -Si(CH3)2-O-, -O - S i ( CH 3 ) 2 - 〇-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane Alkane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, ring Heptadecane ring, cyclooctadecane ring, ring nine yard ring, ring twenty yard ring, three ring twenty yard ring, three ring twenty-two courtyard ring, two-ring heptane ring, decahydronaphthalene ring, original Pentane ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanthene (P hena 1 ene ) ring, fluorene ring, Sodium ring, D-oxazole ring, Thio-P ring, s-ring ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, azole ring, anthracene ring, thiadiazole Ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tenoxo ring, phenanthroline ring, anthracene ring, quin a porphyrin ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, a morpholine ring, etc. X4 may also contain two kinds. The above. There are two or more specific examples, such as -NH-CH2-, -NH-C2H4-, -36-200831611 NH-C3H6·, -NH-C4H8-, -S-CH2-, -S-C2H4 -, -s-c3h6-, -S-C4H8-, -O-CH2-, -O-C2H4-, -0-C3H6-, -O-CzjHg-, -NH-CO-CH2-, -NH-CO -C2H4-, -NH-CO-C3H6-, -NH-CO-C4H8, -CO-CH2-, -CO-C2H4-, -CO-C3H6-, -CO-C4H8-, -CO-NH-CH2· , -co-nh-c2h4-,

-CO-NH-C3H6-, -CO-NH-C4H8-, -NH-CH2-CH(CH3)-, -NH-C2H4-CH(CH3)-, -NH-C3H6-CH (CH3)-, - NH-C4H8-CH (CH3) -, -S-CH2-CH (CH3)-, -S-C2H4-CH (CH3)-, -S-C3H6-CH (CH3)-, -S-C4H8-CH ( CH3) -, -0-CH3-CH (CH3)-, -o-c2h4-ch (CH3), -0-C3H6-CH (CH3)-, -0-C4H8-CH (CH3) -, -NH- CO-CH2-CH ( CH3)-, -nh-co-c2h4-ch ( ch3 ) ·, -NH-CO-C3H6-CH ( ch3 )-, -NH-CO-C4H8-CH ( CH3) -, - CH(OH)-CH2-, -CH(OH)-C2H4-, -CH(OH)-C3H6-, -CH(OH)-C4H8-, -CH(CH2OH)-CH2-, -CH(CH2OH)- C2H4-, -CH(CH2OH)-C3H6-, -CH(CH2OH)-C4H8-, -NH-CH(CH2OH)-CH2-, -CO-NH-CH(CH2OH)-CH2-, -NH-CO- CH ( CH2OH ) -CH2-, -CO-CH ( CH2〇H ) -CH2- , -S-CH ( CH2OH ) -CH2-, -O-CH ( CH2OH ) -CH2-, -CH ( N ( CH3) 2) -, -C6H4-0-, -C6H4-NH-, -C6H4-CO-NH-, -C6H4-NH-CO-, -C6H4-CO-, -C6H4-CH2-, -C 6 η 4 - S -etc. 37-200831611 The oxime 5 of the formula [4] is a nitrogen-containing aromatic heterocyclic ring, which is the same as the oxime 2 of the formula [3], and therefore, Χ5 and Χ2 have the same definitions. Specifically, for example, it has the same configuration as that of the above Χ2. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridyl ring, a pyridinium ring, a guanidine ring, a triple ring, a pyridoxine ring, a triterpene ring, a pyrazine ring, a benzophenone The oxime ring, the m-diazepine ring, the quinoxaline ring, the azepine ring, the dioxetane ring, the naphthyridine ring, the phenazine ring, and the pyridazine ring are preferred. Further, in the case of the ease of interaction between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the specific polyimine, which forms a salt or a hydrogen bond, the enthalpy 4 does not have the formula [8a] contained in Χ5. Preferably, the carbon atoms of the formula [8b] and the formula [8c] are bonded. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X5 in the formula [4] may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain an oxygen atom, a sulfur atom, a nitrogen atom or the like. atom. The preferred combination of X3, X4 and χ5 in the formula [4] is that the χ3 is a linear or branched chain base having a carbon number of 1 to 10, a ring of a propylene ring, a ring of a ring, a ring of a ring, and a ring. Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, original a spinane ring, an adamantane ring, a linear or branched alkyl group having a single bond, a carbon number of 1 to 1 、, -0-, -ΝΗ-, -CO-0-, -〇_c〇-, -CO-NH-, _NH-CO_, -CO_, _S_, _S02...-CF2-, _c (CF3) 2_, -Si (CH3) ”,_0_Si (ch3) 2-, _Si (ch3) 2-0- ' -〇-Si(CH3)2_〇-, -CH(OH)-, _NH-CH2-, _NH-C2H4-, -NH-C3H6-, -NH-C4H8·, S-CH2_, -S-C2H4 -, S-C3H6-> -S-C4H8- '-O-CH2- ' -O-C2H4- - -O-C3H6- N -0-C4H8- ' -38 - 200831611 -NH-CO-CH2-, -NH-CO-C2H4·, -NH-CO-C3H6-, -NH-CO-C4H8' '-CO-CH2· Λ -CO-C2H4- λ -CO-C3H6- ' -CO-C4H8-, -CO -NH-CH2-, -CO-NH-C2H4-, -CO-NH-C3H6-, -CO, NH-C4H8-, -nh-ch2-ch (ch3)-, -NH-C2H4-CH (CH3) -, -NH-C3H6-CH (CH3)-, -NH-C4H8-CH (CH3) -, -S-CH2-CH (CH3)-, -S-C2H4-CH (CH3) - -S-C3H6-CH (CH3)- '

-S-C4H8-CH ( CH3) -, -0-CH3-CH ( CH3)-, -O-C2H4-CH ( ch3 ) -, -0-C3H6-CH ( CH3 )-, -0-C4H8-CH (CH3) -, -NH-CO-CH2-CH (CH3)-, -nh-co-c2h4-ch (CHs) -, -NH-CO-C3H6-CH (CH3)-, -NH-CO-C4H8 -CH(CH3)-, -CH(OH)-CH2-, -CH(OH)-C2H4-, -CH(OH)-C3H6-, CH(OH)-C4H8-, -CH(CH2OH)-CH2- , -CH ( CH2OH) -C2H4-, -CH ( CH2OH) -C3H6-, -CH ( CH2OH) -C4H8-, -NH-CH ( CH2OH) _CH2-, -CO-NH-CH ( CH2OH) -CH2- -NH-CO-CH(CH2OH)-CH2-, -CO-CH(CH2〇H)-CH2-, -S-CH(CH2OH)-CH2-, -O-CH(CH2OH)-CH2-,- CH ( N ( CH3) 2 ) -, -C6H4 〇, -C6H4-NH-, -C6H4-CO-NH-, -C6H4-NH-CO-, -C6H4-CO-, -C6H4-CH2-, -C6H4 -S-, cyclopropane ring, cyclobutyl, cyclopentane ring, cyclohexane ring, cycloheptane ring 'cyclooctane ring, ring 壬 ring, cyclodecane ring, cycloundecyl ring, Cyclododecane ring, raw spinel ring, diamond-39-200831611 alkane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, ring ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanene (Phenalene) Ring, Χ5 is pyrrole ring, imidazole ring, pyridyl Ring, pyridazine ring, pyrimidine D ring, oxime ring, triazine ring, triwax ring, pyrazine ring, benzimidazole ring, m-diazepine ring, quinoxaline ring, azepine ring, Dioxane ring, naphthyridine ring, phenazine ring, pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Χ5 may have a halogen atom and/or an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. 〕中Χ3,Χ4 and combinations thereof, the system Χ3 is selected from the group consisting of carbon number 1~5 direct bond or branch bond base, ring propyl sorrow, Ϊ5 dingyuan ring, cyclopentane ring, cyclohexane ring, cycloglycan An alkane ring, a raw porphyrin ring, an adamantane ring, Χ4 is a linear or branched alkyl group selected from a single bond, having a carbon number of 1 to 5, -0-, ->^-, -CO-O-, - O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -s(o)2-, -ch(oh)-, -nh-ch2-, -s-ch2 -, -o-ch2-, -o-c2h4-, -nh-co-ch2-, -co-ch2-, -co-nh-ch2-,

-NH-CH2-CH(CH3)-, -S-CH2-CH(CH3)-, -0-CH3-CH(CH3)-, -NH-CO-CH2-CH(CH3)-, -CH (OH -CH2-, -CH(OH)-C2H4-, -CH(CH2OH)-CH2-, -NH-CH(CH2OH)-CH2-, -CO-NH-CH(CH2OH)-CH2-, -NH- CO-CH ( CH2OH ) -CH2-, -CO-CH ( CH2〇H ) -CH2- , -S-CH ( CH2OH ) -CH2-, -O-CH ( CH2OH ) -CH2-, -CH (N ( CH3) 2) -, -C6H4-0-, -C6H4-NH-, -C6H4-CO-NH-, -C6H4-NH-CO-, c6h4-co-, -C6H4-CH2--40- 200831611,- CdrS-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, raw spinane ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, ring opening, Anthracycline, anthracene, anthracene, anthracene ring, phenanthrene ring, and phenanene ring X5 are selected from the group consisting of a pyridyl ring, a silane ring, a pyrha ring, a D ring, a pyridazine ring, and a triazine ring. , a triazole ring, a pyrazine ring, a benzimidazole ring, a metadiazonium ring, a quinoxaline ring, a azepine ring, a dioxetane ring, a naphthyridine ring, a phenazine ring, a pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X5 may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. More preferably, the combination of 乂3, 义4 and 乂5 in the formula [4] is a linear or branched alkyl group selected from the group consisting of carbon atoms 1 to 5, a cyclopropane ring, a cyclobutane ring, and a cyclopentane. Ring, cyclohexane ring, X4 is a linear or branched alkyl group selected from a single bond, carbon number 1 to 5, -0-, -NH-, -CO-O-, -O-CO-, -CO -NH-, -NH-CO-, -CO-, -CH(OH)-, -NH-CH2-, -S-CH2-, -o-ch2-, -NH-CO-CH2·, -CO- CH2-, -CO-NH-CH2-, • -NH-CH2-CH(ch3)-, -S-CH2-CH(CH3)-, -0-CH3-CH(CH3)-, -NH-CO- CH2-CH(CH3)-, -CH(OH)-CH2-, -CH(OH)-C2H4-, -CH(CH2〇H)-CH2-, -NH-CH(CH2OH)-CH2-, -CO -NH-CH ( CH2OH) -CH2-, -NH-CO-CH ( CH2〇H ) -CH2-, -CO-CH ( CH2OH ) -CH2- , -S-CH ( CH2OH) -CH2-, -O -CH ( CH2OH) -CH2-, -CH ( N ( CH3) 2) -, C6H4-0-, -C6H4-NH-, -c6h4-co-nh-, -c6h4-nh-co-, -c6h4- Co-, -c6h4-ch2--41 - 200831611, -C6H4-S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, raw spinel ring, adamantane Ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, X5 is selected from pyrrole ring, microphone Ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, indolizine ring between the two. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of & may have a halogen atom and/or an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. The combination of X3, X4 and X5 which is the best in the formula [4] is selected from a linear or branched alkyl group having a carbon number of 1 to 5, a cyclobutane ring and a cyclohexane ring, and is selected from a single bond. -0-, -C0-0-, -0-C0-, -C0.NH·, , -CH(OH)-, benzene ring, naphthalene ring, anthracene ring, anthracene ring, & Imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of χ5 may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. • Specific examples of the specific amine compound used in the present invention, such as a compound of M1 to Μ1 5 6 . -42- 200831611 〔化 23〕

M20

M32 M33 M34 -43- 200831611

H3c, 0

-44- , 0200831611 25] h3c, M68 σ°

M73 NH2

M72

M76

NH2 M77 M78 NH2 F ch3

H3c〆

M80 M79

-45- 200831611 〔化26

M97

M101 M98 M99 M100 nh2 Cl F OH Λ rVCF3 Λ rv V u v nh2 ^nh2 M102 M103 M104 M105 cf3 h,,f3 ΗU,

Ch3 M106 h3c

NH2 h2n M108

M107 M109

M113

M115 n H M116 /V. f 丫, OH [ NH2 N H M117

M118 h2n M119 M120 H 〇 Ml 22

N H

ΝΗ:Ή X:OH M123

N H M124 ύ M121 H h2u M125 46 200831611 〔化 27〕

M126 NH2

M130

~NH2

CH3 N H H3C M133

C CH3 o- M134 M135 M136

O

Η2Νχ/〇 po οςκ M152 M153

, N, CT, NH2 Ml 50 H3C^N,

O M151 M155

Preferred compounds of Mt56 are, for example, M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, Ml 28~Ml 37, Ml 39~M143, Ml 49~Ml 56. More preferably, for example, -47-200831611 M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114~M116, M118~M121, Μ125 'Ml 34~Ml 36, Ml 39, Ml 40, Ml 43 , Ml 50,

Ml 52 to Ml 56 ° <Liquid Crystal Alignment Treatment Agent> The liquid crystal alignment treatment agent of the present invention is usually obtained by mixing a specific polyimine of the above component (A) with a specific amine compound of the component (B) in an organic solvent. be made of. The specific amine compound to be mixed may be one type or several types. The mixing method may use a reaction solution (a solution of a specific polyimine) which is subjected to hydrazylation of a polyamino acid of a specific polyimine precursor, but usually, for example, a specific polyimine obtained by refining A method in which a powder is dissolved in a solution of an organic solvent and a specific amine compound is added. The organic solvent to be used at this time is not particularly limited as long as it is a solution which can dissolve a specific polyimine. This is specifically described below. For example, there are N,N,-dimethylformamide, N,N, dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-caprolactone, 1,3-dimethyl-imidazoledione, Dipentene, ethyl pentanone, methyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethylene carbonate, propylene carbonate, di-linear polyether, 4-hydroxy-4-methyl-2-pentanone and the like. These solvents are also used in combination of -48- 200831611. When a specific polyimine is dissolved in an organic solvent, heating may be performed for the purpose of promoting dissolution of a specific polyimine. When the heating temperature is too high, the molecular weight of the polyimine is lowered, so that the temperature is preferably 30 to 100 ° C, more preferably 50 to 90 ° C. The concentration of the solution of the specific polyimine is not particularly limited. When it is easily mixed with a specific amine compound, the concentration of the specific polyimine in the solution is preferably from 1 to 20% by mass, preferably from 3 to 15% by mass. More preferably, it is preferably 3 to 10% by mass. The specific amine compound may be a solution which can be directly added to the solvent-soluble polyimine, and is preferably added in a suitable solvent to a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is, for example, a solvent of the above solvent-soluble polyimine. It is preferred to heat and mix the specific polyimine with a specific amine compound in an organic solvent or to heat it after mixing. By heating, the ratio of the specific amine compound bonded to the specific polyimine in the state of the liquid crystal alignment agent is increased, and the electromigration movement can be performed more efficiently when the liquid crystal alignment film is formed. The temperature at the time of the above heating is preferably 10 to 10 ° C, more preferably 20 to 80 ° C. The addition amount of the specific amine compound can more effectively obtain the effect of the present invention without impairing the safety of the liquid crystal alignment treatment agent, and the carboxyl group contained in the specific polyimine of 1 mole. 〇 〇 〇 〜 1 ~ 2 Moer times better, better is 〇. 〇 5 ~ 1 Mo, the best is 0.08 ~ 0.8 Mo Er times. The liquid crystal alignment treatment agent of the present invention may contain, in addition to the specific polyimine and the specific amine-49-200831611 compound, a solvent which improves the film thickness uniformity or surface smoothness when coating the liquid crystal alignment treatment agent. Or a compound, a compound which improves the adhesiveness of a liquid crystal alignment film and a board|substrate. Other ingredients may be added during the mixing of the specific polyimine and the specific amine compound, or may be added after mixing the solutions. Specific examples of the solvent for improving the film thickness uniformity or the surface smoothness are as follows. For example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol - 3-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetic acid Ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate , butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropane Ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methoxy-50 - 200831611 -2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate A solvent having a low surface tension such as n-propyl lactate, n-butyl lactate or isoamyl lactate. These solvents may be used in one or a mixture of several. When the above-mentioned solvent is used, it is preferably 5 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent, and more preferably 20 to 60% by mass. A compound which is used to improve film thickness uniformity or surface smoothness, for example, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a nonionic surfactant, or the like. More specifically, for example, Yevtton cloth (transliteration) EF301, EF3 03, EF352 (made by Don Kembroke Guz (trans) company), Mekkafa Valley (transliteration) F171, F173, R-30 (large Japan Ink Company), Fraradon FC430, FC431 (manufactured by Sumitomo 3M), Asa Kayton (AG), Safron (Sound) S-382, SC101, SC102, SC103, SC104, SC10 5, SC106 (made by Asahi Glass Co., Ltd.), etc. The use ratio of the surfactants is preferably 0.01 to 2 parts by mass, more preferably 0. 01 to 1 part by mass, based on the component (A) contained in 100 parts by mass of the liquid crystal alignment agent. Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate are as follows: a functional decane-containing compound or an epoxy group-containing compound -51 - 200831611, for example, 3-aminopropyltrimethoxydecane, 3 -Aminodecane, 2-aminopropyltrimethoxydecane, 2-aminopropane, N-(2-aminoethyl)-3-aminopropyltrimethoxyaminoethyl)-3- Aminopropylmethyldimethoxydecane, methoxydecane, 3-ureidopropyltriethoxydecane, N_: aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-oxo Baseline, N-triethoxymethanealkylpropyltriethylenetrimethylformamidopropyltriethylenetriamine, 10-trimethoxymethyltriazadecane, 10-triethoxymethylidene- 1,4,7-tris-trimethoxycarbamido-3,6-diazaindolyl acetate, decyl-3,6-diazaindolyl acetate, N-benzyl- Methoxydecane, N-benzyl-3-aminopropyltriethoxy-3-aminopropyl methoxy decane, N-phenyl-3-aminodecane, N-bis (oxidation) Ethylene)-3-aminopropyltri-N-bis(ethylene oxide)-3-aminopropyltriethoxyphosphonium oxide Propyl ether, polyethylene glycol diglycidyl ether, propylene glycol dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, propyl ether, 1,6 hexanediol diglycidyl ether, glycerol II Cyclobromonated neopentyl diglycidyl ether, 1,3,5,6-tetraepoxy alcohol, N,N,N',N'-tetraepoxypropyl-m-xylenediamine, two Epoxypropylaminomethyl)cyclohexane, N,N,N,,N' 4,4'-diaminodiphenylmethane, and the like. When such a compound is added, the specific polyamidiene component contained in 100 parts by mass of the liquid crystal is 0.1 to 30 propyl triethoxytriethoxy chopping sand, N - ( 2 -3 - Ureidopropyltriethoxycarbonyl-3-aminopropyltriethylamine, N-trimethoxydecyl-1,4,7-azanonane, 9-9-triethoxymethyl-3-amine Propyltriyldecane, N-phenylpropyl acid ethoxymethoxydecane, alkane, ethylene glycol diglycidyl ether, trisinopentyl epoxide: oxypropyl ether, 2,2-propyl -2,4-hexanedi1,3-1,3-(N,N-tetraepoxypropyl-aligning treatment agent preferably having a mass part of -52-200831611 more preferably 1 to 20 parts by mass. When the amount is 1 part by mass, the effect of improving the adhesion is not obtained, and when it is more than 30 parts by mass, the alignment property of the liquid crystal becomes poor. In the liquid crystal alignment treatment agent of the present invention, the present invention is not impaired except the above. Within the range of the effect, a polymer component other than the specific polyimine or a dielectric or conductive substance for the electrical change of the dielectric constant or conductivity of the liquid crystal alignment film may be added, and the liquid crystal may be formed to be improved. Match The cross-linking compound for the purpose of film hardness or density in the film. The concentration of the solid component in the liquid crystal alignment agent of the present invention can be appropriately changed by the film thickness of the intended liquid crystal alignment film, but no defect is formed. The coating film is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, as the appropriate film thickness of the liquid crystal alignment film. <Liquid alignment film/liquid crystal display element> The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being subjected to baking treatment by a substrate, followed by rubbing treatment or alignment treatment such as light irradiation, or in the case of vertical alignment use or the like without undergoing alignment treatment. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used. In the case of a substrate such as an electrode, it is preferable in terms of simplification of the process, and the reflective liquid crystal display element can be used only on one substrate and an opaque object such as a germanium wafer. In this case, the electrode may be a material such as alumina or the like which reflects light. The method of coating the liquid crystal alignment agent is not particularly limited. In the industry, it is generally screen-printed, off-line, and A method of performing flexographic printing, inkjet, etc. Other coating methods include dipping, roll coating, slit coating, rotator, etc., depending on the purpose, etc. After the liquid crystal alignment treatment agent is applied to the substrate The baking may be carried out by a heating method such as a hot plate at 50 to 200 ° C, preferably 80 to 15 (the solvent is evaporated under TC to form a coating film. The thickness of the coating film after firing is too thick) The power consumption of the liquid crystal display element is extremely unfavorable. When it is too thin, the reliability of the liquid crystal display element is lowered, preferably 5 to 300 nm, and 10 to 100 nm. When the liquid crystal is subjected to horizontal alignment or oblique alignment, the coating film after firing is treated by rubbing or polarized ultraviolet irradiation or the like. In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above method, and a liquid crystal cell is produced by a conventional method to form a liquid crystal display element. For example, when a liquid crystal cell is produced, a substrate on which a pair of liquid crystal alignment films are formed is used, and a spacer is spread on a liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is inside, and the other substrate is pasted. The liquid crystal is injected under reduced pressure _ a method of sealing, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and the substrate is bonded and sealed. At this time, the thickness of the spacer is preferably from 1 to 30 μm, preferably from 2 to 10,111. As described above, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be used for a large-screen, high-definition liquid crystal television or the like. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Examples] The abbreviations used in the examples are as follows.

(tetracarboxylic dianhydride) BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid Dihydride TDA ·· 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (28)

(Diamine) p-PDA : p-phenylenediamine PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene DBA : 3,5-diamino DADPA benzoic acid : 4,4,-diaminodiphenylamine-55- 200831611

DBA DADPA (specific amine compound) 3 - A Μ P · 3 -aminomethyl hydrazine ratio D-defined AEP : 4-(2-aminoethyl)pyridine API : 1-( 3-aminopropyl)imidazole 4 -AMP : 4-aminomethylpyridine 2AMMP : 2-(aminomethyl)-5-methylpyrazine [30]

(Comparative compound) MI : 2-methylimidazole -56- 200831611

Py : 啦b VPy : 2-vinyl pyridine

ΑΡΜΑ : N-( 3-aminopropyl)-N-methylaniline ΑΡ : 3-aminopyridine ΗΑ : n-hexylamine

H2N-C6H13

HA (organic solvent)

NMP : N-methyl-2-pyrrolidone BCS : butyl cellosolve GBL : γ-butyrolactone < molecular weight determination of polyimine > The molecular weight of the polyimine of the synthesis example, using a new repair Scientific company system room temperature gel permeation chromatography (GPC) device (SSc

7200), Shodex company column (KD-803, KD805), inY F is described for measurement.

Column temperature: 50 °C Dissolution: N, N, - dimethylformamide (with lithium bromide ~ outer eight e (-57- 200831611

LiBr-H20) is 30 mmol/L, phosphoric acid anhydrous crystals (〇_phosphoric acid) is 30 mmol/L, and tetrahydrofuran (THF) is 10 ml/L) as an additive) Flow rate: 1.0 mL/min. : TSK standard polyethylene oxide (molecular weight about 9,000, 150,000, 100,000, 3 〇〇〇〇) manufactured by Dongsuo Co., Ltd., and polymer Labrador (trans) company, the amount of polyethylene glycol is about 12,000, 4,000 , 1,000). <Measurement of ruthenium iodide> The ruthenium imidization ratio of polyimine in the synthesis example was as follows. 2 Omg of polyimine powder was added to an NMR sample tube (NMR by Kusano Scientific Co., Ltd.) The sample tube starter φ 5 ), 0.53 ml of dimethyl hydrazine dihydrogen hydride (DMSO-d5, 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve the solution. The solution was made by the Japanese electronic Ditham Company. The NMR measuring device (INW-ECA500) was used to measure the proton NMR at 500 MHz. The azylation rate of the yttrium Φ was determined by using protons from a structure that did not change before and after the imidization as a reference proton, and the peaks of the protons were used. The proton peak enthalpy of the NH group of the amino acid present in the vicinity of 9.5 to 10.Oppm is obtained by the following formula: 醯 imidization ratio (%) = ( · x / y ) X 1 00 In the above formula, x is the proton peak cumulative enthalpy derived from the NH group of the amino acid, y is the peak cumulative enthalpy from the reference proton, and α is the i-58-200831611 polyamino acid (醯imination) The ratio of the number of the reference protons in the proton of the NH group of the amino acid at the rate of 〇%). The method for determining the amount was determined by the method described above. (Synthesis Example 1) BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 6 3 mm ο 1 ), PCH (10.3 g, 27 mmol) was mixed in NMP (100.g), and after reacting at 40 ° C for 3 hours, c BDA ( 4 · 1 g, 2 1 mm o 1 ) and NMP ( 5 2.2 g ) were added at 40°. The reaction was carried out for 3 hours at C to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (1 3 0.3 g), diluted to 6 mass%, and acetic anhydride (1 5 · 6 g ) was added. Pyridine (1 2 · 1 g ) was used as a ruthenium catalyst to carry out a reaction at 80 ° C for 3 hours. The reaction solution was poured into methanol (1 600 ml), and the resulting precipitate was filtered. The mixture was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyamidimide had a ruthenium imidation ratio of 54%, a number average molecular weight of 18,300, and a weight average molecular weight. It is 45,300. The amount of the carboxyl group of the polyimine is 0.92 for the repeating unit. (Synthesis Example 2) BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol), PCH (10. 3 g, 2 7 mmol ) in NMP ( 100 0g) mixed, after fT reaction at 40 ° C for 3 hours, 'CBDA (4.1g, 21mmol -59-200831611) and NMP (52.2g) were added, and the reaction was carried out at 40 °C for 3 hours to obtain polyfluorene. Amino acid solution. NMP was added to the polyamic acid solution (55.4 g), and after diluting to 6 mass%, acetic anhydride (2.7 g) and pyridine (2.1 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 70 ° C. 1 hour. The reaction solution was poured into methanol (660 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The polyimine had a hydrazine imidization ratio of 25%, a number average molecular weight of 19,500, and a weight average molecular weight of 47,800. The amount of the carboxyl group of the polyimine was 1.50 for the repeating unit. (Synthesis Example 3) BODA (1 50.1 g, 600 mmol), DBA (60.9 g, 400 mmol), PCH (152.2 g, 400 mmol) were mixed in NMP (1290 g), and the reaction was carried out at 80 ° C for 5 hours, and then added. CBDA (38.8 g, 198 mmol) and NMP (3 20 g) were reacted at 40 ° C for 3 hours to prepare a polyaminic acid solution. Into the polyaminic acid solution (600.2 g), Ν Μ P was added, and after diluting to 6% by mass, acetic acid drunk (6 3 · 9 g ) and pyridin (49.6 g) were added as a ruthenium amide catalyst. The reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (7700 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had a ruthenium iodide ratio of 57%, a number average molecular weight of 23,000, and a weight average molecular weight of 80,200. The amount of the carboxyl group of the polyimine is 1.36 for the repeating unit. -60 - 200831611 (Synthesis Example 4) BODA (50.1 g, 600 mmol), DBA (60.9 g, 400 mmol), PCH (152.2 g, 400 mmol) were mixed in NMP (1 290 g), and the reaction was carried out at 80 °C. After the hour, CBDA (38.8 g, 198 mmol) and NMP (320 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (30O.lg) and diluting it to 6 mass%, acetic anhydride (32.0 g) and pyridine φ (24.8 g) were added as a ruthenium catalyzed catalyst at 90 ° C. The reaction was carried out for 2.5 hours. The reaction solution was poured into methanol (3900 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (D). The polyimine had a hydrazine imidation ratio of 69%, a number average molecular weight of 22,700, and a weight average molecular weight of 69,300. The amount of the carboxyl group of the polyimine was 1.12 for the repeating unit. (Synthesis Example 5) BODA (150.lg '600 mmol), DBA (60.9 g, 400 mmol), and PCH (152.2 g, 40 mmol) were mixed in NMP (1 2 9 0 g), and the mixture was carried out at 80 ° C. After reacting for 5 hours, CBDA (3 8.8 g, 1 98 mmol) and NMP (3 20 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (101.2 g) and diluting it to 6 mass%, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 90 ° C. 3 hours. The reaction solution was poured into methanol (1 300 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C. -61 - 200831611 to obtain a polyimine powder (E). The polyimine had an oxime imidization ratio of 81%, a number average molecular weight of 20,400, and a weight average molecular weight of 63. The amount of the carboxyl group of the polyimine is 〇.88 for the repeating unit. (Synthesis Example 6) BODA (16.0 g, 64 mmol), DAD PA (H*9 g 60 mmol), PCH (9.7 g, 26 mmol) were mixed in NMP (126.4 g), and the reaction was carried out at 40 ° C for 3 hours. Thereafter, CBDA (3.8 g, 19 mmol) and NMP (40 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (5 〇. 3 g), and after diluting to 4% by mass, acetic anhydride (5.0 g) and pyridin (3.9 g) were added as a ruthenium catalyst, at 50 The reaction was carried out at ° C for 2 hours. The reaction solution was poured into methanol (91 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (F). The polyamidimide had a ruthenium iodide ratio of 25% φ, a number average molecular weight of 22,200, and a weight average molecular weight of 69,000. The amount of the carboxyl group of the polyimine was 1.50 for the repeating unit. (Synthesis Example 7) BODA (7.5 g, 30 mmol), DADPA (1.6 g, 8.0 mm ο 1 ), DBA (2.4 g, 16 mmol), PCH (6.1 g, 16 mmol) in NMP (5 3.2 g ) After mixing and reacting at 40 ° C for 3 hours, CBDA (1.9 g, 10 mmol) and NMP (25 g) were vigorously introduced, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. Add NMP to the polyamine-62 - 200831611 amino acid solution (60.4g), dilute to 5% by mass, add acetic anhydride (6 · 3 g ), pyridine (4 · 9 g ) as ruthenium amide catalyst The reaction was carried out at 90 ° C for 2 hours. The reaction solution was poured into methanol (8 80 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (〇). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 21,100, and a weight average molecular weight of 64,000. The amount of the carboxyl group of the polyimine was 1.38 for the repeating unit. (Synthesis Example 8) TDA (9.0 g, 30 mmol), DBA (3.2 g, 21 mmo 1 ), p-PDA (1.0 g, 9.0 mmol) were mixed in NMP (74.7 g), and the reaction was carried out at room temperature. In hours, a polyaminic acid solution was prepared. After adding NMP to the polyamic acid solution (80.0 g) and diluting it to 6% by mass, acetic anhydride (2 9 · 1 g ) and pyridine (1 3 · 5 g ) were added as a ruthenium-based catalyst. The reaction was carried out at 3 ° C for 3 hours. The reaction solution was poured into methanol (7 μm ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (Η). The polyamidimide had a ruthenium imidation ratio of 91%, a number average molecular weight of ιυοο, and a weight average molecular weight of 20,570. The amount of the carboxyl group of the polyimine was 0.88 for the repeating unit. (Example 1) NMP (41.9 g) was added to the polyimine powder (a) (7.4 g - 63 - 200831611) obtained in Synthesis Example 1, and stirred at 80 ° C for 40 minutes to dissolve. To the solution, 7.5 14.8 g of 3_AMP (as 3-AMP, 1.1 L), NMP (3.7 g), 55.5 g) was added, and the mixture was stirred at 50 ° C for 15 hours to prepare a liquid crystal formulation (1). . <Production of Liquid Crystal Cell> The liquid crystal alignment treatment agent (1) obtained above was spin-coated on a glass substrate coated with an ITO electrode, and dried on a hot plate at 80 ° C to obtain a hot air of 2 10 ° C. A liquid crystal alignment film having a film thickness of 100 nm was fired in a circulating oven for 1 hour. Two sheets of the liquid crystal alignment plate were used, and a sealant was printed on a liquid crystal alignment film of one of them, and the sealant was printed thereon, and the sealant was hardened to produce a cell. In the empty cell, a liquid crystal ML C-Meru Valley (manufactured by Nippon Co., Ltd.) was injected by a vacuum injection method to seal the injection port and the liquid crystal cell. When the liquid crystal cell was observed under a polarizing microscope, the liquid crystal was uniformly aligned, and there was no alignment defect. <Evaluation of voltage holding ratio> The voltage of the liquid crystal cell produced above was measured at a temperature of 80 ° C, a voltage of 4 V, 60 μδ, and after 16.67 ms and after 166 7 ms, the voltage was maintained as a voltage holding ratio. As a result, the retention rate of 16.67 ms was 97.6%, and the voltage retention rate of 1 667 ms was 67.3%. At the time of the solution (BCS (to the treatment for 5 minutes, after making the base of the film, for the air crystal 6608 (the pressure is applied to the ground vertically, the voltage is -64-200831611 and the measurement system uses the Toyo Digu The VHR-1 voltage retention rate measuring device manufactured by Nika Corporation is measured at a setting of Voltage: ±4V, Pulse Width: 60ps, Flame Period: 16.67ms or 1667ms. <Evaluation of Residual Charge Mitigation> A voltage of 10 V for 30 minutes was applied to the liquid crystal cell after the voltage holding ratio measurement, and a short circuit occurred for 1 second, and then a potential generated in the liquid crystal cell was measured for 1 800 seconds. The potential change at this time is as shown in Fig. 1. As a result, the residual charge after 50 seconds after the short circuit was 3.19 V, and the residual charge after 1 000 seconds was 0.25 V. Further, the measurement was performed using a 6254 liquid crystal physical property evaluation device manufactured by Toyo Digunik Co., Ltd. Evaluation after high-temperature placement> The liquid crystal cell which was subjected to the above measurement was placed in a thermostat set at 100 ° C for 7 days, and the same measurement was performed. As a result, the voltage retention rate of 16.67 ms was 97.8%, 1 66 The voltage retention rate of 7 ms was 67.2%, the residual charge after 50 seconds was 3.41 V, and the residual charge after 1 000 seconds was 0.46 V. (Example 2 to Example 1 8) The liquid crystal alignment treatment agent was prepared as follows (2) ~(1 8 ), a liquid crystal cell was produced and evaluated in the same manner as in Example 1. In all of the unit cells, the liquid crystal was uniformly aligned vertically, and there was no alignment defect. The evaluation results are shown in Tables 1 and 2 below. -65-200831611 (Example 2) A liquid crystal alignment treatment agent (2) was prepared in the same manner as in Example 1 except that the polyimine powder (B) obtained in Synthesis Example 2 was used. The liquid crystal alignment treatment agent (3) was prepared in the same manner as in Example 1 except that the polyimine powder (C) obtained in Synthesis Example 3 was dissolved by stirring at 7 ° C for 40 hours. (Example 4) NMP (30.6 g) was added to the polyimine powder (C) (5.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to dissolve. Add 3-AMP 1% by mass NMP solution (5.4g) (as 3-AMP, 0.38g), NMP (8.1g), BCS (4 0.5g), at 50 The liquid crystal alignment treatment agent (4) was obtained by stirring at ° C for 15 hours. (Example 5) By adding NMP (30.6 g) to the polyimine powder (C) (5.4 g) obtained in Synthesis Example 3. The mixture was stirred at 70 Torr for 40 hours to dissolve. To this solution, a 7 mass% hydrazine solution (5.4 g) (as 3-AMP, 〇.38 g), NMP (8.1 g), BCS (40.5 g) was added to the solution, and the mixture was stirred at 50 ° C. In the hour, a liquid crystal alignment treatment agent was prepared (5-66-200831611 (Example 6). By adding NMP (41.9 g) to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, at 70 The mixture was stirred for 40 hours at ° C to dissolve. A solution of 5-AMP in NMP (7.4 g) (as 3-AMP, 0.37 g), NMP (ll.lg), BCS (55.5 g) was added to the solution. The mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (6 (Example 7) by adding NMP to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3. (41.9 g) was dissolved by stirring at 70 ° C for 40 hours. A solution of 8.5% by mass of NEP (14.8 g) (as AEP, 1.26 g), NMP (3.7 g), and BCS (ACS) was added to the solution. 5 5.5 g ), stirring at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (7 ). (Example 8) By using the polyimide pigment (C) obtained in Synthesis Example 3 ( Add NMP (41.9g) to 7.4g) and stir at 70 °C It was dissolved in 40 hours. To the solution was added API 1% by mass NMP solution (I2.5g) (as API, 1.26g), NMP (5.9g), BCS (55.5g), at 50 °C. The liquid crystal alignment treatment agent (8) was prepared by stirring for 15 hours. -67-200831611 (Example 9) By adding NMP (57.8 g) to the polyimine powder (D) obtained in Synthesis Example 4, Stirring was carried out at 70 ° C for 40 minutes. To the solution was added 3-AMP 3 mass % NMP 1 0.2 g ) (as 3-AMP, 0.31 g), NMP (6.8 g), 8 5 · 0 g ) The mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal formulation (9 ) 〇 (Example 1 〇) by adding NMP to the polyamidamine powder (D) obtained in Synthesis Example 4. (57.8 g), stirred at 70 ° C for 40 minutes to dissolve. To the solution, 5-AMP-5 mass% NMP (10 g) (as 3-AMP, 0.51 g), NMP (6.8 g), and 85.0 g) was added, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal. Agent (10). (Example 11) NMP (57.8 g) was added to the polyimine powder (D) obtained in Synthesis Example 4, and stirred at 70 ° C for 40 minutes to dissolve. To this solution, 7 mass% of NAMP 1 〇. 2 g ) (as 3 - A Μ P, 0.7 1 g ), N Μ P (6 · 8 g ), 85.0 g) was added at 50 ° C. The mixture was stirred for 15 hours to obtain a liquid crystal formulation (1 1 ). (10.2 g of the solution (BCS) (to the treatment (10.2 g of the solution (BCS (to the treatment (10.2 g of the solution (BCS (to the treatment -68-200831611 (Example 1 2) by using Synthesis Example 4 To the obtained polyimine powder (D)), NMP (57.8 g) was added, and stirring was carried out at 70 ° C for 40 minutes. To the solution, 10 mass % of NAMP (10 mass %) was added to the solution (as a 3- AMP, l. g), NMP (6.8 g), 8 5.0 g), stirring at 50 ° C for 15 hours to obtain a liquid crystal formulation (12). (Example 1 3 ) NMP (42.0 g) was added to the polyimine powder (E) obtained in Synthesis Example 5, and stirred at 70 ° C for 40 minutes to dissolve. 7 % by mass of 3 - A Μ P was added to the solution Ν Μ P Solution) (as 3-AMP, 0.6g), NMP (2.4g), :BCS (', stirring at 50 ° C for 15 hours to obtain liquid crystal alignment treatment (Example 14)) NMP (42.0 g) was added to the polyimine powder (E) obtained in Synthesis Example 5, and stirred at 70 ° C for 40 minutes to dissolve. To the solution, 10 mass % of NMP (8.6 g of 3-AMP) was added ( As 3-AMP, 0.86g) > NMP (2.4g), 7 1 · 7 g ) The liquid crystal formulation (14) was prepared by stirring at 50 ° C for 15 hours. (A solution was prepared at 10.2 g (BCS) (treated to 8.6 g (8.6 g r1.7 g) (13 g (8.6 g) Time to solution (BCS (to treatment -69-

200831611 (Example 1 5) NMP (41.9 g) was added at 80 by the polyimine powder (F) obtained in Synthesis Example 6. (: 40 times of stirring under stirring. Add 10 mass of 3-AMP to /1 1 ^ 1 1 .1 g ) (as 3-AMP, l.llg), NMP (7.4g), 55.5g The mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal formulation (15) 〇 (Example 16) by using the polyimine powder (G) obtained in Synthesis Example 7.

NMP (41.9 g) was added thereto, and the mixture was stirred at 80 ° C for 40 minutes to dissolve. To this solution, 3-AMP 5 mass% NMP solution (as 3-AMP, 0.37 g) 'NMP (11 lg), :BCS) was added, and the mixture was stirred at 50 ° C for 15 hours to obtain a solution. Liquid crystal alignment (solution at 7.4g (BCS (to treatment (7.4g (55.5g (55.5g)

(Example 1 7) NMP (42.0 g) was added to the polyimine powder (E) obtained in Synthesis Example 5, and stirred at 80 ° C for 40 minutes to dissolve. To this solution, 4-AMP 7 mass% NMP solution (as 4-AMP, 〇.6g), NMP (2.4g), and BCS (' were stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment (8-6 g of (8 · 6 g r 1.7 g) agent (17 - 70 - 200831611 (Example 18) by using the polyimine powder (E) obtained in Synthesis Example 7 (8.6 g) NMP (42.0 g) was added thereto, and the mixture was stirred at 80 ° C for 40 hours to dissolve. 2MMP of 7 mass% NMP solution (8.6 g) (as 2AMMP, 0.6 g) and NMP (2.4 g) were added to the solution. BCS (71.7 g) was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (1 8 ). (Comparative Example 1) By the polyimine powder (A) obtained in Synthesis Example 1 ( NMP (41.9 g) was added to 7.4 g of the solution, and the mixture was stirred at 80 ° C for 40 hours to dissolve. NMP (18.5 g) and BCS (55.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment. Using the liquid crystal alignment treatment agent, a liquid crystal cell was produced and evaluated in the same manner as in Example 1. When the liquid crystal cell was observed with a polarizing microscope, the liquid crystal was uniformly aligned vertically, and In the case of the alignment defect, <Evaluation of voltage holding ratio> When the voltage holding ratio was measured in the same manner as in Example 1 in the liquid crystal cell produced as described above, the voltage holding ratio of 16.6 ms was 97.4%', and the voltage holding ratio of 1667 ms was 64.1. -71 - 200831611 <Evaluation of Residual Charge Relaxation> The liquid crystal cell after the measurement of the voltage holding ratio was evaluated in the same manner as in Example 1 to evaluate the residual charge relaxation, and the residue after 50 seconds after the short circuit The electric charge was 2.63 V, and the residual electric charge after 1 000 seconds was 0.61 V. <Evaluation after high temperature standing> The liquid crystal cell having the above measurement was completed in the same manner as in Example 1, Φ was set at 1 〇〇 ° C After 7 days in the constant temperature bath, the voltage holding ratio and the residual charge relaxation were evaluated. As a result, the voltage retention of 16.67 ms was 97.2%, the voltage retention of 1 667 ms was 57.7%, and the residual charge after 50 seconds was 4.33 V. The residual charge after 1.000 seconds was 2.62 V. (Comparative Example 2 to Comparative Example 8) Liquid crystal alignment treatment agents (20) to (26) were prepared as described below, and a liquid crystal cell was produced in the same manner as in Example 1. All liquid crystal cells Uniformly vertically aligned liquid crystal, no alignment defect situation using a liquid crystal cell produced in the same method as in Example 1, a voltage holding ratio, relaxation of the residual charge, and the evaluation of high-temperature place. The evaluation results are as shown in Tables 1 and 2 below. (Comparative Example 2) NMP (41.9 g) was added to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to be dissolved in -72 - 200831611. NMP (1 8 · 5 g ) and B C S (5 5 · 5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (20). (Comparative Example 3) A liquid crystal alignment treatment agent was prepared in the same manner as in Example 3 except that Py was used instead of 3-AMP, and Py (0.81 g) was mixed with the polyimine powder (C) (7.4 g). twenty one ). (Comparative Example 4) A liquid crystal alignment treatment agent (22) was obtained in the same manner as in Example 3 except that hydrazine was used instead of 3 amp. (Comparative Example 5) A liquid crystal alignment treatment agent (23) was obtained in the same manner as in Example 3 except that MI was used instead of 3_AMp. (Comparative Example 6) A liquid crystal alignment treatment agent (2 4 ) was obtained in the same manner as in Example 3 except that VPy was used instead of 3_AMp. (Comparative Example 7) The same procedure as in Example 3 was carried out except that the mixed liquid crystal alignment agent was replaced with 3-AMP' using AP 7.4 g) and the polyimine powder (c) (AP (1.2 6 g ) was used. (25) -73-200831611 (Comparative Example 8) A liquid crystal alignment treatment agent (2 6 ) was obtained in the same manner as in Example 3 except that HA was used instead of 3-AMP.

Polyimine amine compound voltage retention rate (%) 16.67 ms 1667 ms 16.67 ms 1667 ms after high temperature placement in liquid crystal cell preparation Example 1 A 3-AMP 97.6 67.3 97.8 67.2 Example 2 B 3-AMP 97.0 53.0 96.7 52.0 Example 3 C 3-AMP 97.8 63,5 97.7 63.6 Example 4 C 3-AMP 97.8 64.6 97.9 64.3 Example 5 C 3-AMP 97.8 64.1 97.9 65.0 Example 6 C 3-AMP 97.8 64.8 97.8 60.9 Example 7 C AEP 97.5 61.0 97.4 62.7 Example 8 C API 97.3 62.5 97.3 68.6 Example 9 D 3-AMP 98.1 68.3 98.0 68.2 Example 10 D 3-AMP 98.1 68.2 98, 1 68.1 Example 11 D 3-AMP 98.0 68.0 98.0 68.1 Example 12 D 3-AMP 98.1 68.0 98.1 68.0 Example Π E 3-AMP 98.0 68.2 98.1 68.3 Example 14 E 3-AMP 97.8 67.8 98.0 67.8 Example 15 F 3-AMP 97.5 54.1 97.7 56.3 Example 16 G 3-AMP 97.8 67.8 98.1 67.8 Example 17 E 4-AMP 98.1 68.6 98.2 68.5 Example 18 E 2AMMP 98.1 67.2 98.0 67.4 Comparative Example 1 A - 97.4 64.1 97.2 57.7 Comparative Example 2 C - 97.8 62.6 97.6 63.1 Comparative Example 3 C Py 97.8 63.6 97.6 62.3 Comparison Example 4 c ΑΡΜΑ 96.6 31.5 96.7 31.6 Comparative Example 5 c MI 96.9 50.5 96.8 48.9 Comparative Example 6 c VPy 97.6 64.0 97.7 64.0 Comparative Example 7 c AP 97.6 62.4 97.5 62.6 Comparative Example 8 c HA 97.3 64.2 97.2 64.0 -74- 200831611

Table 2 Relaxation of Residual Charge of Polyimine Amine Compound (V) Liquid Crystal Crystal 1 妄 After preparation of high temperature after 50 seconds, after 1000 seconds, after 50 seconds, and after 1000 seconds, Example 1 A 3-AMP 3.19 0.25 3.41 0.46 Example 2 B 3-AMP 2.96 0.17 1.47 0.19 Example 3 C 3-AMP 2.61 0.25 1.28 0.30 Example 4 C 3-AMP 1.54 0.15 1.39 0.24 Example 5 C 3-AMP 2.94 0.17 2.21 0.48 Example 6 C 3-AMP 3.05 0.17 2.01 0.41 Example 7 C AEP 1.47 0.14 1.13 0.23 Example 8 C API 2.99 0.17 1.26 0.28 Example 9 D 3-AMP 3.04 0.34 2.76 1.13 Example 10 D 3-AMP 3.02 0.25 2.29 0.64 Example 11 D 3-AMP 2.77 0.20 2.75 0.62 Example 12 D 3-AMP 2.87 0.25 2.54 0.59 Example 13 E 3-AMP 3.26 0.22 3.34 1.15 Example 14 E 3-AMP 3.18 0.30 2.84 0.80 Example 15 F 3-AMP 1.94 0.18 1.62 0.34 Example 16 G 3-AMP 2.29 0.16 2.38 0.58 Example 17 E 4-AMP 3.21 0.26 3.19 1.07 Example 18 E 2AMMP 3.15 0.28 3.17 0.97 Comparative Example 1 A - 2.63 0.61 4.33 2.62 Comparative Example 2 C - 2.21 0.66 3.68 1.88 Comparative Example 3 C Py 2.18 0.67 3.72 1.74 Comparative Example 4 C ΑΡ Α 2.60 0.73 3.90 2.36 Comparative Example 5 C MI 2.83 0.65 3.83 1.85 Comparative Example 6 C VPy 3.07 0.60 3.72 2.12 Comparative Example 7 C AP 2.64 0.55 3.64 2.42 Comparative Example 8 C HA 2.97 0.68 3.91 2.38 [Industrial Utilization Price] The present invention The liquid crystal alignment agent has a high voltage holding ratio, and after a long time exposure at a high temperature of -75 to 200831611, a liquid crystal alignment film which relaxes the residual charge by the DC voltage can be obtained. Therefore, the liquid crystal display element ’ thus obtained can suppress the display failure of the screen burnt or the display spot even if it is used for a long period of time, and can be suitably used for a large-screen, high-definition liquid crystal television or the like for excellent reliability. Moreover, the liquid crystal display element can be suitably used for various display devices. In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract description of the Japanese Patent Application No. 2 〇 06_2 0661, filed on Jul. 28, 2006, which is incorporated herein by reference. Brief Description of the Drawings [Fig. 1] shows a potential change diagram when the relaxation of residual charge is evaluated in the first embodiment. -76-

Claims (1)

200831611 X. Patent Application No. 1. A liquid crystal alignment treatment agent characterized by containing the following components (A) and (B), (A) component: polyimine having a carboxyl group in a molecule, and (B) component An amine compound having one primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. (2) The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the component (A) is imidized by a polyamic acid formed by a structural formula having a repeating unit represented by the following formula [1]. The polymer, the amount of carboxyl groups of the polymer, the average unit of the repeating unit of the polymer is 〇.1~3, [Chemical 1] (In the formula, Ri is a tetravalent organic group, R2 is a divalent organic group, and η is a positive integer). 3. The liquid crystal alignment treatment agent according to claim 1, wherein the component (A) is such that a part or all of the repeating unit in the structural formula of the repeating unit represented by the formula [1] has the following formula [ 2] The polyamine acid formed by the structural formula of the unit is subjected to a ruthenium imidized polymer, and the carboxyl group amount of the polymer has an average enthalpy of 0.1 to 3 -77 - [ 2] 200831611 [Chemical 2] The organic group, R3 or an amine compound in the liquid crystal alignment, at least one of r4 has a carboxyl group). 4. The IJ agent according to any one of claims 1 to 3, wherein the component (B) is represented by the following formula [3] [3] (wherein X 1 is an aliphatic hydrocarbon group or a non-aromatic® valent organic group, and X 2 is a nitrogen-containing aromatic heterocyclic ring). 5. The JJ agent according to any one of claims 1 to 4, wherein the component (B) is represented by the following formula [4] (Chemical Formula 4) ^X3 / X5 H2Z [4] (wherein the χ3 system The aliphatic hydrocarbon group having a carbon number of 1 to 1 Torr, the hydrocarbon group, and the X4 is a divalent organic group of a single bond, -0-, -NH-, -S-, -SO: and a carbon atom of X3 and X4; 20, X5 is a nitrogen-containing aromatic hetero compound which may have a substituent. 6. A liquid crystal alignment amine compound of the liquid crystal alignment cyclic hydrocarbon group of claim 5, non-aromatic ring- or carbon Numbers 1 to 19: Total measurement is 1 to ring). The treatment agent, wherein -78 - 200831611 (B) is an amine compound selected from the group consisting of Χ3, Χ4 and X5 of the formula [4], each selected from the group or ring combination described below. a straight or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring , cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, ring fifteen ring, ring sixteen Ring, ring seventeen yard ring, ring eighteen yard ring, ring φ nineteen alkane ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, decahydrogen a group consisting of a naphthalene ring, a raw spinel ring, and an adamantane ring; the Χ4 system is one selected from the group consisting of a single bond, _〇..._ΝΗ•, -s_, -S〇2, a carbon number of 19, and c Ο - 〇-, - 〇_ c Ο -, - c Ο - N Η -, - N Η - C Ο -, - C Οι -CF2- , -c ( CF3) 2_ ... CH ( OH) - , - c ( CH3) 2- , -Si ( CH3) 2-, -〇, Si ( ch3) 2-, -Si ( CH3 ) 2-〇-, -Ο-Si ( CH3 ) 2-0-, cyclopropane Ring, cyclobutane ring, cyclopentane ring, cyclohexene k ring, heptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, ring eleven ring, cyclododecane ring, ring ten a trioxane ring, a cyclotetradecane ring, a ring of fifteen rings, a ring of sixteen, a ring of seventeen (four), a decane ring, a cyclopentadecane ring, a cyclododecan ring, a tricyclohexadecane ring, Tricyclotetracosane ring, dihheptane ring decahydronaphthyl ring, raw spinane ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, blessing; ^ TM ItaI 绐, Do not Ring, ϊ ϊ, phenanthrene ring, phenanthene (e) cyclopyrrolidine ring, oxime ring, oxa π ring, thiazide ring, pyrazole pyridine ring I pyridine ring, quinoline ring, pyrazoline Ring, isoquinoline ring, indazole ring, anthracene ring, thiophene~ Μ * - soil S咕ί哀, 哒嚓ί哀, triazine 擐, _ alkane 擐, -79- 200831611 — wow &, pyrazine a ring, a benzimidazole ring, a phenanthroline ring, an anthracene ring, a quinoxaline ring, a benzothiazole ring, an acridine ring, an oxazole ring, a piperazine ring, and a morphine ring The group X5 formed by the group or several combinations is one selected from the group consisting of pyrrole ring, imidazole ring and oxazole. , pyridine ring, pyrimidine ring, quinoline ring, pyrazolidine ring, haha ring, thiadiazole ring, pyridazine ring, pyr Φ pyrazolidine ring, triazole ring, pyrene ring, benzoquinazoline Dino A group of a ring of a porphyrin ring, a phenanthroline ring, an anthracene ring, a quinoxaline phenothiazine ring, an oxadiazole ring, an acridine ring, and the like. 7. The application agent in the scope of the patent scopes i to 6, wherein the polymer of 1 mole (A) component is contained in a ratio of 〇·〇1 to 2 moles (8. In the first to seventh aspects of the patent range, the poly-imine of (A) is heated and mixed or mixed in an organic solvent. 9. A liquid crystal alignment film characterized by The liquid crystal display element obtained by any one of the liquid crystal alignment agents of any one of the above-mentioned items, wherein the liquid crystal display element is characterized by the liquid crystal alignment film of the ninth item. Anthracene ring, tenoxo ring, azole ring, phenothiazine Ring, piperidine ring, dioxane ring I ring, thiazole ring, hydrazol ring, isoquinoline ring, oxazoline ring, triazine ring, ring, meta-diaza ring, ring, benzothiazole ring, Any one of the liquid crystals may have a carboxylic acid: B) component contained in the imine. One liquid crystal alignment: B) the amination of the component is heated and obtained. Patent Van-80-