TW200948859A - Liquid-crystal alignment material and liquid-crystal display element made with the same - Google Patents

Abstract

Provided is a liquid-crystal alignment material giving a liquid-crystal alignment film which has a high voltage retention and which, even after long-term exposure to a high temperature, retains the property of quickly diminishing a residual charge accumulated by a direct-current voltage. Also provided is a liquid-crystal display element having the liquid-crystal alignment film. The liquid-crystal alignment material comprises a copolymer obtained by reacting a diamine ingredient comprising a diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride. Diamine compound (A): a diamine compound represented by the following formula [1] Diamine compound (B): a diamine compound having a carboxy group in the molecule (Chemical formula 1) [1] (In the formula [1], X1 is at least one divalent organic group selected from the group consisting of -O-, -NQ1-, -CONQ1-, -NQ1CO-, -CH2O-, and -OCO-; Q1 is hydrogen or C1-3 alkyl; X2 is a single bond or at least one divalent organic group selected from the group consisting of C1-20 aliphatic hydrocarbon groups, nonaromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups; X3 is a single bond or at least one divalent organic group selected from the group consisting of -O-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO-, and -O(CH2)m- (m is an integer of 1-5); Q2 is hydrogen or C1-3 alkyl; X4 is a nitrogenous aromatic heterocycle; and n is an integer of 1-4.)

Description

[Technical Field] The present invention relates to a physicochemical agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] At present, the liquid crystal alignment film of the liquid crystal display element is mainly a polyimine precursor of A phthalic acid or a liquid crystal alignment treatment agent of a main component of soluble polyamidiamine (also referred to as a liquid crystal alignment glass substrate). The so-called polyamidene-based liquid crystal alignment film which is fired is used to control the alignment state of the liquid crystal. However, with the high definition of the liquid crystal display element, the suppression or afterimage of the contrast reduction of the element is shown. In the liquid crystal alignment film to be used for image reduction, it is necessary to increase the voltage holding ratio, or to apply Φ to reduce the residual charge, and/or to moderate the characteristics of the charge due to the DC voltage. The polyimine-based liquid crystal alignment film is gradually added. In the case of shortening the time until the disappearance of the DC residual image, it is known that a third-order agent having a specific structure other than polyamine containing polyamidamine is used (for example, refer to Patent Document 1), or used in A solution of a soluble polyimine of a specific diamine such as a pyridine skeleton (for example, see Patent Document 2). Further, as a residual image caused by a DC voltage, the residual image disappears. For the purpose of coating the liquid crystal alignment film with the liquid solution in the liquid crystal alignment, the liquid crystal alignment is used to make the proline acid or the amine-containing liquid crystal compound which is generated by the residual voltage accumulated at the DC voltage. It is known that a compound having a crystal alignment agent has a high retention rate, and it is known that a compound having a carboxyl group selected from a molecule having a minimum amount of a molecule other than poly-proline or a ruthenium imidized polymer thereof is used. A liquid crystal alignment agent containing a compound of one carboxylic acid anhydride group and a compound containing one compound of a tertiary amino group in the molecule (for example, see Patent Document 3). However, in recent years, large-screen and high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements for such applications are more demanding than the remaining ones in comparison with display applications that have mainly displayed characters or still pictures. It is demanding and requires long-term use in an environment of excessively harsh use. Accordingly, the liquid crystal alignment film used also requires higher reliability than in the past, and the electrical characteristics of the liquid crystal alignment film not only require good initial characteristics, but also require, for example, long-term exposure even at high temperatures. Maintain good characteristics. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the liquid crystal alignment film is used as a liquid crystal alignment film, the liquid crystal alignment treatment agent for the liquid crystal alignment film which retains the residual electric charge accumulated by the DC voltage can be used as early as possible when exposed to a high temperature for a long period of time. Provided is a liquid crystal display element which has a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent and which is resistant to long-term use in a severe use environment. The present inventors have conducted intensive investigations for the above purposes and found that -6-.200948859 can achieve the liquid crystal alignment treatment agent for this purpose. The present invention is based on the results, and has the following features. (1) A liquid crystal alignment treatment agent characterized by 'a copolymer containing a diamine component (A) and a diamine compound (B) and a tetrahydro acid dianhydride component, a diamine compound ( A): a diamine compound represented by the following formula: (II): a diamine compound having a carboxyl group in the molecule '[Chemical 4]

(In the formula [i], again! is at least one divalent organic group selected from the group consisting of a 〇-, an NQ1-, a CONQ1-, - NQiCO-, -CH20-, and -OCO-, Q1 is a hydrogen atom Or an alkyl group having a carbon number of 1 to 3 'I is a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. Χ3 is a single bond or is selected from the group consisting of _〇_, one NQ2-, -CONQ2—, -NQ2C0—, —C00—, —OCO—and —〇(CH2)m—(m is an integer from 1 to 5) At least one divalent organic group 'Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X4 is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4). (2) The liquid crystal alignment treatment agent of the above (1) wherein the formula Π is at least one selected from the group consisting of the compounds represented by the following formulas [la] to [If] 200948859 Η

Χ2-Χ3-Χ4) η νη2 ¥〇-χ2-χ3-Χ4) η Χ2-Χ3-Χ4) η

(wherein Q1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and χ2 is a single bond or at least selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. A divalent organic group, Χ3 is a single bond or selected from — NQ2—, —CONQ2-, —NQ2CO—, —COO—, —OCO—and a 〇(CH 2 ) m— ( rn is an integer from 1 to 5) At least one of the groups is a divalent organic group, Q2 is a hydrogen atom or a carbon number! to an alkyl group of 3, χ4 is a nitrogen-containing aromatic heterocyclic ring, and η is an integer of 1 to 4. (3) The liquid crystal alignment treatment agent according to the above (2), wherein the oxime 2 in the formula [la] to the formula [If] is a single bond, a linear alkyl group having 1 to 3 carbon atoms or benzene is bad. (4) The liquid crystal alignment treatment agent according to (2) or (3) above, wherein χ3 in the formula [la] to the formula [lf] is a single bond, _〇c〇- or -〇CH2 - 〇 (5) The liquid crystal alignment treatment agent according to any one of the above (2) to (4) wherein the oxime 4 in the formula [1&] to the formula [lf] is an imidazole ring, a pyridine ring or a pyrimidine ring. The liquid crystal alignment treatment agent according to any one of the above (2) to (5), wherein, in the formula [la] to the formula [if]! ! is an integer of i or 2. (7) The liquid crystal alignment treatment agent according to the above (2), wherein X2 in the formula [la] to the formula [If] is a linear or branched alkyl group selected from a carbon number of 1 to 1 fluorene, and cyclohexane. At least one of a ring, a benzene ring and a naphthalene ring, X3 being selected from the group consisting of a single bond, a 0-, a CONH-, an NHCO-, a COO-, -OCO-, and -0 (CH2:U- (m) At least & of the group of 1 to 5), X4 is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a sorghum ring, a three-pound ring, a triazole ring, and a piperidine. And a liquid crystal alignment treatment agent according to the above (2), wherein the formula [la] to the formula [the formula [la] to the formula [2] is a mixture of the pyridine ring, the benzimidazole ring, and the benzimidazole ring. If 2 in If] is at least one selected from the group consisting of a single bond, a straight or branched alkyl group having 1 to 5 carbon atoms, and a benzene ring selected from the group consisting of a single bond, -0-, a CONH-, and At least one of NHCO-, one COO-, one OCO-, and -0(CH2)m- (m is an integer from 1 to 5), X4 0 is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, and a pyridine At least one of a group of a ring and a pyrimidine ring, and η is 1 or 2 (9) The liquid crystal alignment treatment agent according to the above (2), wherein the oxime 2 in the formula [la] to the formula [If] is a linear alkyl group selected from a single bond, a carbon number of 丨 to 3, and a benzene ring. At least one of the groups, χ3 is at least one selected from the group consisting of a single bond, an OCO-, and -OCH2, and χ4 is at least one selected from the group consisting of an imidazole ring, a pyridyl ring, and a pyrimidine ring, η (1) The liquid crystal alignment treatment agent according to any one of the above (1) to (9) wherein the diamine compound having a carboxyl group in the molecule is the following formula [2] 200948859 The diamine represented, [chemical 5] h2n

[2] (In the formula [2], X5 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.] (1 1 ) The liquid crystal according to the above item (1) An alignment treatment agent, wherein the diamine compound of the formula [2] is at least one diamine compound selected from the group consisting of the following formulas [3] to [7],

-10- 200948859 化 H2N-^ -irtCOOH) [3] (CHzWCOOHΗ2Ν"0~{Ό"νΗ2(CH2)m5^〇〇H [5]

(CH2)m6COOH

[6]

(In the formula [3], ml is an integer from 1 to 4 in the formula [4], 'X6 is a single bond, -CH2- ' -C2H4- ' - C(CH3)2- ' - CF2- ' ❹ _c (cf3 ) 2—, — Ο — ' — CO — ' - ΝΗ —, — N(CH3)— '—CONH— ' — NHCO — ' — CH2〇 — ' — OCH2 — ' — COO-, - OCO - , - CON (CH3)-, or -N(CH3)CO-, m2 and m3 are integers from 〇 to 4, respectively, and ni2+m3 represents an integer from 1 to 4, and in the formula [5], m4 and m5 are 1 to 5, respectively. In the integer 'Formula [6], 'X? is a linear or branched alkyl group having a carbon number of 1 to 5, and m6 is an integer of 1 to 5. In the formula [7], 'χ8 is a single bond, a CH2—, a C2H4 -, a C(CH3)2 -, a CF2, a C(CF3)2-, - 〇-, - CO -, - ΝΗ -, - Ν (CΗ3), a CONH-, - NHCO-, a CH20—, — OCH2-, -11 - 200948859 -COO -, an OCO-, -CON(CH3)-, or an n(ch3)co-, m7 is an integer from 1 to 4. (12) The liquid crystal alignment treatment agent according to the above (11), wherein, in the formula [3], ml is an integer of 1 to 2. (13) The liquid crystal alignment treatment agent according to the above item (11), wherein, in the formula [4], 'X6 is a single bond, a CH2—, a C2H4—, a C(CΗ3) 2 , a Ο _ , _ CΟ —, a ΝΗ _, a N(CΗ3)—, —CONH —, —NHCO —, —COO —, or —OCO—, m2 and m3 are integers of one at the same time. (14) The liquid crystal alignment treatment agent according to the above item (11), wherein, in the formula [7], X8 is a single bond, a CH2-, a 0-, a _CO-, a -NH-, a CONH-, a NHCO-, -CH20-, -OCH2-, -COO-, or -OCO-, m7 is an integer from 1 to 2. The liquid crystal alignment treatment agent according to any one of the above-mentioned (1) to (1), wherein the diamine component has a molar amount of 1 mol relative to the diamine represented by the formula, in the molecule. The diamine having a carboxyl group is from 0.01 to 99 moles. The liquid crystal alignment agent of any one of the above-mentioned (1) to (15), wherein 5 to 80% by mass of the solvent contained in the liquid crystal alignment treatment agent is a weak solvent. The liquid crystal alignment treatment agent according to any one of the above aspects, wherein the copolymer in the liquid crystal alignment treatment agent is a polyimine obtained by dehydration ring closure of polyacrylic acid. (18) A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of the above (1) to (7). -12- 200948859 (19) A liquid crystal display element comprising the liquid crystal alignment film of (18) above. The liquid crystal alignment treatment agent of the present invention can be obtained by a relatively simple method, and when the liquid crystal alignment treatment agent is used, a high voltage retention ratio can be obtained, and even when exposed to a high temperature for a long time, the DC voltage can be moderated earlier. A liquid crystal alignment film that accumulates residual charges. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has excellent reliability and is highly suitable for use in a liquid crystal television having a large screen and high definition. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a liquid crystal alignment agent comprising a copolymer obtained by reacting a diamine component comprising a diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent, And a liquid crystal display element having the liquid crystal alignment film. In this case, the diamine compound (A) is a diamine compound represented by the formula [1], and the diamine compound (B) is a diamine compound having a carboxyl group in the molecule. The diamine compound (A) used in the present invention is one in which a branched chain has a nitrogen-containing aromatic heterocyclic ring. The nitrogen-containing aromatic heterocyclic ring has a function of hopping-site due to its conjugated structure, and promotes the movement of charges in the liquid crystal alignment film. Further, the nitrogen-containing aromatic heterocyclic ring is bonded to the carboxyl group of the diamine compound (B) via electrostatic interaction forming a salt or a hydrogen bond, thereby causing a charge between the carboxyl group and the nitrogen-containing aromatic heterocyclic ring.产-13- 200948859 生移动. Therefore, the charge moved to the nitrogen-containing aromatic heterocyclic moiety can be efficiently moved intramolecularly or intramolecularly in the copolymer. For the above reasons, the liquid crystal alignment treatment agent of the present invention can obtain a high voltage holding ratio when used as a liquid crystal alignment film, and can repel the residual electric charge accumulated by the DC voltage even when exposed to a high temperature for a long period of time. The effect. <Diamine component> [Diamine compound (A)] The diamine compound (A) used in the present invention is a diamine compound represented by the following formula [1]. [Chemistry 7]

Nh2 H2N {·Χι-X2-X3-X4 ) n [ 1 ] In the formula [1], again! Is at least one divalent organic group selected from the group consisting of -〇-, -NQ1-, -CONQ1-, -NQko-, -CH20-, and -OCO-, and Q1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms X2 is a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group, and X3 is a single bond or is selected from a 0-, - NQ2-, -CONQ2-'-NQ2CO-'-COO-'-0C0- and -〇(CH2)m- (m is an integer from 1 to 5) of at least one divalent organic group, Q2 is a hydrogen atom Or an alkyl group having a carbon number of 1 to 3 'X4 is an aromatic heterocyclic ring having a nitrogen content of from 14 to 200948859, and n is an integer of from 1 to 4. The bonding position of the two amine groups (mono-2) in the formula [1] is not limited. Specifically, when η is an integer of 1, it is exemplified by a bonding group (Xj) with respect to a side chain, 2, 3 positions on the benzene ring, 2, 4 positions, 2, 5 positions '2, ό position, 3, 4 position, 3, 5 position. When η is an integer of 2, the following positions are exemplified. With respect to the bonding group of the side chain (Χι ), when the side of the benzene ring has a side chain bonding group (χι), the bonding position of the two amine groups is exemplified by 3, 4 positions '3, 5 positions'. 3, 6 position, 4, 5 position. Further, when the side chain bonding group (X,) is present at the 3 position on the benzene ring with respect to the bonding group (Xi) of the side chain, the bonding position of the two amine groups is exemplified by 2, 4 positions, 2 5 position, 4, 5 position, 4, 6 position. Further, when the bonding group (X!) having a side chain at the 4-position on the benzene ring is bonded to the bonding group (X!) of the side chain, the bonding positions of the two amine groups are exemplified by the positions 2 and 3, 2, 5 position, 2, 6 position, 3, 5 position. When η is an integer of 3, the following positions are exemplified. With respect to the bonding group (X!) of the side chain, when the bonding group (Xi) having a side chain at the positions 2 and 3 on the benzene ring, the bonding positions of the two amine groups are exemplified by 4, 5 positions, 4 , 6 positions. Further, when the bonding group (X!) having a side chain at the positions 2 and 4 on the benzene ring is bonded to the bonding group (X,) of the side chain, the bonding position of the two amine groups is exemplified as 3, 5 Position, 3, 6 position, 5, 6 position. Further, when the side chain bonding group (X i ) has a side chain bonding group (X!) at the 3 and 5 positions on the benzene ring, the bonding positions of the two amine groups are exemplified by 2 and 4 positions. . When n is an integer of 4, the following positions are exemplified. With respect to the bonding group of the side chain ( Χι ), when the bonding group (Xi) of the side chain is present at the 2, 3, and 4 positions on the benzene ring, the bonding positions of the two amine groups are exemplified by the 5 and 6 positions. Further, when the bonding group (X!) of the chain is present at the 2, 4, and 5 positions on the benzene ring with respect to the bonding group (Xi) of the chain of the 200948859 chain, the bonding position of the two amine groups is exemplified as 3 , 6 positions. Further, when the bonding group (X!) having a side chain at the positions 2, 4, and 6 on the benzene ring is bonded to the bonding group (X!) of the side chain, the bonding position of the two amine groups is exemplified as 3, 5 position. Among these, the viewpoint of the reactivity in synthesizing poly-proline, and the ease of synthesizing the diamine compound, when η is an integer of 1, the bonding position of the two amine groups is preferably 2 , 4 position, 2, 5 position, 3, 5 position, or η is an integer of 2 with respect to the binding group (Xi) of the side chain, and has a side chain bonding group at the 3 position on the benzene ring (X〇, The bonding position of the two amine groups is preferably 4 and 6. The formula [1] is selected from the group consisting of a 〇-, an NQ1-, a CONQ1-, an NQkO-, a CH20-, and an -OCO. At least one divalent organic group of the group, wherein _〇_, one NQ1-, -CONQ1-, one; KQkO- is preferred. Moreover, the Q1 system is the same as the definition of the formula [1]. X! More specific structure For example, the following formula [la] to formula [If]. [Chemical] H2丨

H2

X2-X3-X*) n Η,

-Χ2-Χ3-Χ4)η [1 f] 〇

H2I

ΓΓ2 gas [lc]

-16- 200948859 wherein, the formula [la], the formula [lb], the formula [〗 〖], and the formula [Id] are preferred. Further, Q1 is the same as the definition of the formula [1]. In the formula [1], x2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic aromatic hydrocarbon group, or an aromatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Further, it may have an unsaturated bond. Specific examples of the aliphatic hydrocarbon group fluorene non-aromatic cyclic hydrocarbon group preferably having 1 to 10 carbon atoms are exemplified by a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane. Alkane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, ring Heptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cycloecosane ring, tricyclohexadecane ring, tricyclodecane ring, bicyclobutane ring, decahydronaphthalene ring, norbornene ring , adamantane ring, etc. Specific examples of the aromatic hydrocarbon group are a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an Austrian ring, a pitch ring, an anthracene ring, a ring, a phenanthrene ring, and a Phenalene ring. In the formula [1], preferred X2 is a single bond, a linear 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, and a cyclopentane. Alkane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, more preferably a single bond, carbon number 1 to 10 Straight chain or branched alkyl, carbon number 1 to 10 unsaturated extension base, ring ring ring, original borneol ring, diamond ring, benzene ring, naphthalene ring, ring, ring, and better It is a single bond, a linear or branched carbon number of 1 to 1 -17. -17- 200948859 alkyl, cyclohexane, benzene, naphthalene ring, especially a single bond, straight chain or branch of carbon number 1 to 5. Extend the base and benzene ring. It is preferably a single bond, a linear alkyl group having a carbon number of 1 to 3 or a benzene ring. In the formula [1], χ3 is a single bond or is selected from -NQ2-,

—0(CH 2 ) m — (m is an integer of 1 to 5) at least one divalent organic group 'preferably a single bond, —〇—, a C0NQ 2−, —nQ 2 c〇—, —COO —, — OCO- and —〇(CH2)m — (m is an integer from 1 to 5). It is preferably a single bond, an OCO- or -〇CH2-. And the 'Q2 system is the same as the definition of the formula [1]. In the formula [1], x4 is a nitrogen-containing aromatic heterocyclic ring, and is a nitrogen-containing compound containing at least one structure selected from the group consisting of the following formula [2 a], the formula [2b], and the formula [2 c]. Aromatic heterocycle. [Chemical 3]

' Y! in the formula [2 c] is a linear or branched alkyl group having 1 to 5 carbon atoms. In the formula [1], preferred X4 is 13⁄4: a slightly ring, a oxime ring, a chewable 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, tower ring, oxazoline ring, three-till ring, pyrazolidine ring, triazole ring, piperidine ring, benzimidazole ring, benzimidazole ring, tino Phytoline ring, phenanthroline ring, anthracene ring, quinolino ring, benzo-18-.200948859 thiazole ring, phenothiazine D ring, oxadiazole ring, azetidine ring, more preferably pyrrole ring, imidazole ring, pyridyl Oxazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, oxazole ring, sorghum ring, pyrazoline ring, three-till ring, pyrazolidine ring, triazole ring, piperidine ring, benzimidazole ring, benzene And an imidazole ring, more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a sorghum ring, a three-till ring, a triazole ring, a piperidine ring, a benzimidazole ring, a benzimidazole ring, Preferably, it is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. Further preferably, it is an imidazole ring, a pyridine ring or a pyrimidine ring. Further, X3 is preferably bonded to a substituent which is not adjacent to the formula [2a], the formula [2b] and the formula [2c] contained in X4. In the formula [1], η is an integer of 1 to 4, and is preferably an integer of 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride. Preferably, η is an integer of 1 or 2. The preferred combination of X, Χ2, Χ3, Χ4 and η in the formula [1] is X, which is selected from the group consisting of -NQ1-, -CONQi-, -NQiCO-, -CH20 - and - oco - at least one of the group, χ2 is selected from a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, and a ring. a group consisting of a butane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, and an anthracene ring. At least one type, χ3 is a single bond or at least selected from the group consisting of -0_, _NQ2-, -CONQ2, -NQ2CO-, -COO-, an OCO-, and (111 is an integer from 1 to 5) X4 is selected from the group consisting of pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, -19-200948859 miso ring, 嘌呤Ring, thiadiazole ring, sorghum ring, pyrazoline ring, three-till ring, scorpion steep ring, triazole ring, piperidine ring, benzimidazole ring 'benzimidazole ring, quinololine ring, phenanthroline Ring, anthracene ring, quinololine ring, stupid A thiazole ring, a phenanthrene ring lake thiazole, oxadiazole ring and azetidine ring at least one of the groups, [eta] is an integer of 1 or 2. Preferably, the combination of Xi, Χ2, Χ3, 4 and η in the formula [1] is Xl selected from at least one group consisting of one 〇—, one NQi_, one CONQ1-, one NQkO—and —CH2〇— And x2 is a linear or branched alkyl group having a carbon number of 1 to 10, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, At least one of a group consisting of a naphthalene ring, an anthracene ring and an anthracene ring, the hydrazine 3 is selected from the group consisting of a single bond, a fluorene-, -NQ2-, a CONQ2-, -NQ2CO-, -COO-, -OCO- and a quinone (CH2)m—(m is an integer from 1 to 5) at least one of the group, and X4 is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, an indazole ring, At least one of a group consisting of a sorghum ring, a pyrazoline ring, a tri-negative ring, a pyrazolidine ring, a triazole ring, a piperidine ring, a benzimidazole ring, and a benzimidazole ring, and η is an integer of 1 or 2. Further, the combination of Xi, Χ2, Χ3, Χ4 and η in the formula [1] is X! is selected from the group consisting of -〇_, -NQi-, -CONQi-, -NQiCO-, a CH20-, and a 0C0- At least one of the groups, x2 is at least one selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring, and X3 is selected from a single bond, X0 -, -C0NQ2-, - NQ2C0-, - C00-, -0C0-, and -0(CH2)m - (m is an integer from 1 to 5) are at least one group, X4-20-200948859 is selected At least one of a group of a free pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a fluorene D ring, a three-till ring, a triazole ring, an acridine ring, a benzimidazole ring, and a benzimidazole ring. η is an integer of 1 or 2. Preferably, the combination of Χι, Χ2, Χ3, Χ4 and η in the formula [1] is at least one selected from the group consisting of one 〇, one NQi-, one C; 〇NQi_, one----CH20-. Χ2 is at least one selected from the group consisting of a single bond, a linear or branched alkyl group having a carbon number of 1 to 5, and a benzene ring selected from the group consisting of a single bond, a 0-, a C0NQ2-, and an NQ2CO- And -C00-, -0C0- and -0(CH2)m- (m is an integer from 1 to 5) in groups of at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine At least one of the groups of the rings, η is an integer of 1 or 2. Further, the combination of Χι, Χ2, Χ3, Χ4, and η in the formula [1] is X, which is selected from -0-, an NQ1-, At least one of a group of C0NQ1- and -NQiCO-, X2 is at least one selected from the group consisting of a single bond, a linear alkyl group having 1 to 3 carbon atoms, and a benzene ring, and X3 is selected from a single bond, - 0C0 - and -0CH2 - at least one of the group, X4 is at least one selected from the group consisting of an imidazole ring, a pyridine ring and a pyrimidine ring, and n is an integer of 1 or 2. The combination of Χι, Χ2, Χ3, Χ4 and η in the best formula is shown in Tables 1 to 3 below. Further, Q1 and Q2 are the same as defined in the formula [1]. -21 - 200948859 [Table i]

Xl X2 χ3 X4 Al -0- single bond single bond imidazole ring A-2 -0- single bond single bond pyridine ring A-3 -0- single bond single bond pyrimidine ring A-4 —NQ1 — single bond single bond imidazole ring A-5 -NQ1- single bond single bond pyridine ring A-6 -NQ1- single bond single bond pyrimidine ring A-7-CONQ1 — single bond single bond imidazole ring A-8 -CONQ1- single bond single bond port ratio steep ring A-9 -CONQ1- single bond single bond pyrimidine ring A-10 -NQ^O- single bond single bond imidazole ring A-ll -nq'co- single bond single bond pyridine ring A-12 _NQ]CO- single button Aminopyrimidine ring A-13 -0- a linear alkyl group having a carbon number of 1 to 3, an imidazole ring A-14 —Q — a linear alkyl group having a carbon number of 1 to 3, a pyridine ring A-15-o - a straight-chain alkyl-monomethylpyrimidine ring having a carbon number of 1 to 3, A-16 -0- a linear alkyl group having a carbon number of 1 to 3, a 0C0-imidazole ring, A-17 -0-, and a carbon number of 1 to 3 Linear alkyl-0C0-pyridine ring A-18 — 0 — linear alkyl 1C to 10-C0-pyrimidine ring A-19-0- straight chain alkyl group having 1 to 3 carbon atoms Och2-imidazole ring A-20 -0 - linear alkyl 1 to 3 - och2 - ca ring A-21 -0 - linear alkyl 1 - 3 - och 2 - pyrimidine ring A -22 -NQ 1-Carbon number 1 to 3 linear alkyl group single bond imidazole ring A-23 -NQ1 carbon number 1 to 3 linear alkyl group single bond shaky steep ring A-24 -NQ1- carbon number 1 to 3 Linear one-chain alkyl single-bonded pyrimidine ring A-25 -NQ1- straight-chain alkyl-C0-C0-imidazole ring A-26 -NQ1- linear alkyl-alkyl group having 1 to 3 carbon atoms 0C0- mouth ratio π ring A-27 -NQ1 - 1 to 3 carbon chain alkyl-Oc0-pyrimidine ring A_ 28 -NQ1 - 1 to 3 straight chain alkyl-och2 - imidazole ring A-29 -NQ1 - straight chain alkyl-och2 of carbon number 1 to 3 - pyridine ring A-30 -NQ1 - linear alkyl group of 1 to 3 carbon atoms -och2-pyrimidine ring A-31 -CONQ1- Linear one-chain alkyl single bond imidazole ring of carbon number 1 to 3-22-200948859 Table 2]

Xl X2 χ3 X4 A-32 -CONQ1- linear one-link alkyl single bond of carbon number 1 to 3 than steep ring A-33 A CONQ1- linear one-chain alkyl single bond pyrimidine ring A- 34 -CONQ1- Linear 1 -3 linear alkyl-OCO-imidazole ring A-35 -CONQ1- linear 1 to 3 linear alkyl-C0- pyridyl ring A-36 -CONQ1- carbon 1 to 3 linear alkyl-alkyl-C0-pyrimidine ring A-37-CONQ1- straight-chain alkyl group having 1 to 3 carbon atoms -och2-imidazole ring A-38 -CONQ1- carbon number 1 to 3 Chain alkyl-och2—mouth ratio steep ring A-39 -CONQ1- linear chain alkyl 1 to 3 och2-pyrimidine ring A-40 -NQ^O- linear extension of carbon number 1 to 3 Alkyl single bond imidazole ring A-41 -NQ^O- straight chain alkylene single bond ring of carbon number 1 to 3 A-42 -NQJCO- linear alkyl one-bonded pyrimidine of carbon number 1 to 3 Ring A-43 -nq'co- Linear alkyl 1C0-Imidazole ring A-44 -NQ^O- straight chain alkyl-C0-pyr ring of carbon number 1 to 3 A-45 -NQ^O- Linear alkyl 1C0-pyrimidine ring A-46 -nq!co- 1 to 3 linear alkyl-och2-imidazole ring A- 47 -NQ^O- Linear alkyl-och2-pyrene with 1 to 3 carbon atoms Ring A—48 -NQ^O- Linear alkyl-o-och2-pyrimidine ring A-49 —0- phenyl ring single bond imidazole ring A-50 -0- benzene ring single bond pyridine ring A -51 -0- phenyl ring single bond pyrimidine ring A-52 -0- benzene ring-0C0- imidazole ring A-53 -0 — benzene ring-0C0- shame steep ring A-54 -0- benzene ring-0C0-pyrimidine Ring A-55 -0- phenyl ring-och2-imidazole ring A-56 -0- benzene ring-och2- 陡 steep ring A-57 -0- phenyl ring-och2-pyrimidine ring A-58 -NQ1- benzene ring Key imidazole ring A-59 -NQ1- benzene ring single bond pyridine ring A-60 -NQ1- benzene ring single bond pyrimidine ring A-61 -NQ1-benzene ring-0C0-imidazole ring A-62 -NQ1-benzene ring-0C0 - 咖定环-23- 200948859 Table 3]

Xl X2 X3 X4 A-63 -NQ1-benzene ring-OCO- pyrimidine ring A-64 -NQ1-benzene ring-och2-imidazole ring A-65 -NQ1-benzene ring_ OCH2 _ mouth ratio steep ring A-66 - NQ1-benzene ring-OCH2- squirrel ring A-67-CONQ1- benzene ring single bond imidazole ring A-68 —CONQ1- lysing single bond port ratio steep ring A-69 -CONQ1- Lai single bond pyrimidine ring A-70 -CONQ1- benzene ring -OCO-Imidazole ring A-71 -CONQ1- Benzene ring-OCO-pyridine ring A-72 -CONQ1- benzene ring-OCO-pyrimidine ring A-73 -CONQ1-benzene ring-och2-imidazole ring A-74 -CONQ1- Benzene ring-OCH2- sister D-ring A-75-CONQ1-benzene ring-och2-pyrimidine ring A-76-NQ^O- benzene ring single bond imidazole ring A-77 -NQ*CO- benzene ring single bond Ring A-78 -NQ^O- phenyl ring single bond pyrimidine ring A-79 -NQ^O- benzene ring-OCO- imidazole ring A-80 -NQ^O- benzene ring-OCO- pyridine ring A-81 -NQ ^O- phenyl ring-OCO-pyrimidine ring A-82 -NQ^O- phenyl ring-och2-imidazole ring A-83 -nq'co- benzene ring-OCH2- port specific ring A-84 -nq'co- Benzene ring-OCH2-pyrimidine ring A-85-CONQ1 — phenyl ring single bond imidazole ring A-86 -CONQ1- benzene ring single bond D ratio steep ring A-87 -CONQ1- benzene ring single bond pyrimidine ring A-88 -CONQ1 - Benzene ring-OCO- Imidazole ring A-89 -CONQ1- benzene ring-OCO- pyridine ring A-90 -CONQ1- benzene ring-OCO-pyrimidine ring A-91 -CONQ1-benzene ring-och2-imidazole ring A-92 -CONQ1-benzene ring - OCH2 _ lyon ring A-93 -CONQ1 - benzene ring _ OCH2 _ pyrimidine ring-24- 200948859 [Synthesis method of monoamine compound (A)] The method for producing the diamine compound represented by the formula [1] of the present invention is not Particularly limited 'but the preferred method is listed below. [Chemistry 9]

The specific diamine compound of the present invention is obtained by synthesizing a dinitro group represented by the formula [4], followed by reduction conversion of a nitro group to an amine group. The method for reducing the dinitro compound is not particularly limited, and is usually carried out by using a catalyst such as palladium-carbon, uranium oxide, ruthenium nickel, platinum black, ruthenium-alumina, or platinum sulfide carbon in ethyl acetate or toluene. Among the solvents such as tetrahydrofuran, dioxane, and alcohol, hydrogen, hydrazine, hydrogen chloride, and the like are used. X!, X2, X3, X4 and η in the formula [4] are the same as defined in the formula [1]. The dinitro group of the formula [4] can be bonded to the ruthenium 2 and the ruthenium 4 through the Χ3 bond, and then the dinitro moiety is bonded to the ruthenium 2 through the χι linkage through the Χι bond, and then bonded through the Χ3 and Χ4. The method and the like. Χι is selected from the group consisting of - (ether bond), -NQ1 - (amino bond), -CONQ1 - (melamine bond), -NQkO - (reverse amine bond), -CH20 - (methylene ether bond) And at least one bonding group in which 〇C〇-(anti-ester bond) is grouped, and the bonding group can be formed by a usual organic synthesis method. The Q1 system of each bonding group is the same as the definition of the formula Π]. For example, in the case where Χι is an ether or a methylene-branched bond, 'exemplification is a method of reacting a dinitro-containing halogen derivative corresponding to 200948859 with a hydroxy derivative containing ruthenium 2, X3 and X4 in the presence of a base' or A method of reacting a dinitro group-containing hydroxy derivative with a halogen-substituted derivative containing ruthenium 2, osmium 3 and ruthenium 4 in the presence of a base. The case of the amino group bond is exemplified by a method of reacting a corresponding halogen derivative containing a dinitro group with an amine derivative containing ruthenium, iridium 3 and ruthenium 4 in the presence of a base. In the case of the reverse ester bond, 'exemplified by the method of reacting the corresponding dinitro group-containing derivative with a ruthenium containing ruthenium 2, ruthenium 3 and 4 in the presence of a base, in the case of a guanamine bond' The method of reacting the corresponding dinitro-containing ruthenium chloride with the amine substituent containing ruthenium 2, ruthenium 3 and X4 in the presence of a base is exemplified by the case of a reversed urethane bond. A method in which a base substituent is reacted with a ruthenium chloride containing ruthenium 2, osmium 3, and ruthenium 4 in the presence of a base. Specific examples of the dinitro group-containing halogen derivative and the dinitro group-containing derivative are exemplified by 3,5-dinitrochlorobenzene, 2,4 dinitrochlorobenzene, and 2,4-dinitrofluorobenzene. , 3,5-dinitrobenzhydryl chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzylidene chloride, 2,4-dinitrobenzoic acid, 3,5_2 Nitrobenzyl chloride, 2,4 dinitrosyl chloride, 3,5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5 -dinitroaniline, 2,6-dinitroaniline, 2,4-dinitroguanidine, 2,5-dinitroguanidine, 2,6-dinitrophenol, 2,4-dinitrobenzene Acetic acid and the like. Considering the availability of raw materials, -26-200948859, one or more of them can be selected. [Diamine compound (B)] The diamine compound (B) used in the present invention has a diamine compound having a residue in the molecule. The specific structure thereof is not particularly limited, and is preferably a compound represented by the formula [2]. [化10]

In the formula [2], X5 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and η is an integer of 1 to 4. When the formula [2] is represented by a specific example, the structures of the following formulas [3] to [7] can be cited. [化11]

I nh2

WCOOH

(CH2)m5COOH

(CH2)meCOOH (CH2)meCOOH

H2 Η2ΝΌΧβί^Χ8〇·ΝΗ2

-27- 200948859 In the formula [3], ml is an integer from 1 to 4, and in the formula [4], X6 is a single bond, —C Η 2 — ' — C 2 Η 4 —, a C (C Η 3 ) 2 —,~ c F 2 ~, —C(CF3)2 —, one Ο—, one CO—, one NH _, one N (C Η 3)—, —CONH— ' — NHCO— ' — CH2〇— ' — OCH2— ' -coo—, — oco —, — con(ch3)— ' or -n(ch3)co- , m2 and m3 are integers from 0 to 4, respectively, and m2+m3 represents an integer from 1 to 4. In the formula [5], m4 and m5 are each an integer of 1 to 5 in the formula [6], and X7 is a linear or branched alkyl group having a carbon number of 1 to 5 'm6 is an integer of 1 to 5' [7] ] 'X8 is a single bond, -CH2—, —C2H4_, one C(CH3)2_, _CF2 —, one C(CF3)2—′′—Ο—, —CΟ—, —ΝΗ—, one N(CH3) —, a CONH-, an NHCO-, a CH2〇-, an OCH2-, -COO-, - OCO-, -CON(CH3)-, or a N(CH3)CO-, m7 is an integer from 1 to 4. . In the structure of the formula [3] to the formula [7], 'preferably, in the formula [3], ml is an integer structure of 1 to 2, in the formula [4], X6 is a single bond, a CH2-, -C2H4- , -C(CH3)2— ' — ο- ' - CO— ' — NH— ' — N(CH3)— ' -CONH -, - NHCO -, - COO -, or a 〇CO— ' m2 and m3 simultaneously In the structure of an integer of 1, in the formula [7], X8 is a single bond, a CH2 —, —〇—, _ c〇-, —NH —, —CONH —, —NHCO —, —CH20— ' - OCH2- ' — COO-, or a 0C0_, m7 is a structure of integers from 1 to 2. Specific examples of the diamine compound (B) are, for example, compounds of the following formula to the formula [18]. 200948859 〇 [Chem. 12]

Η2ν

In the formula [17], Χ9 is a single bond, a CH2-, a 0-, -CO-, -NH-, a CONH-, an NHCO-, a CH20-, an OCH2-, a -COO-, or a OCO—, in the formula [18], Xi. It is a single bond, _ CΗ2 one, one 〇 _, _ CΟ one, _ ΝΗ one, one CONH — , —NHCO −, one CH20 —, one OCH 2 —, one COO —, or —OCO —. [Other diamine compound] 29-200948859 In the present invention, a diamine compound other than the diamine compound (A) or the diamine compound (B) can be used as a diamine component without impairing the effects of the present invention. . Specifically, it is shown below. p-Toluenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl a monophenylene diamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diamino Phenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3, 3'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy- 4,4 '-Diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4' Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiyl Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino 2 Ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine , bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl) ) decane, 4,4' monothiodiphenylamine, 3,3'-monodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4 'monodiaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diamino) Phenyl)amine, N-methyl (3,3'-diamine-30-200948859-diphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl)amine, :^-methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3, 3'-Diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3' Monoaminobenzophenone, 1,5-diaminonaphthalene, 1,6- Amino naphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2 ,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-amino Phenyl)propane, 1,3_bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl) Alkane, bis(3,5-diethyl_4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3_bis(4-aminophenoxy) Benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1, 3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylphenylbis(methylene)]diphenylamine, 4,4'-[1,3-phenylene (methylene)]diphenylamine, 3,4' _[1,4 phenylphenylbis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene) Diphenylamine, 3,3'-[1,4-phenylphenylbis(methylene)]diphenylamine, 3,3'-[1,3-phenylphenylbis(methylene)]diphenylamine, 1 , 4 Phenyl bis[(4-aminophenyl)methane], 1,4_phenylene bis[(3-aminophenyl)methane], 1,3-phenylene bis[(4-amino group) Phenyl)methane], 1,3-phenylenebis[(3-aminophenyl)methane], 1,4-phenylphenylbis(4-aminobenzoate), 1,4 phenylene Bis(3-aminobenzoic acid ester), 1,3_phenylene bis(4-aminobenzoate), 1,3_-31 - 200948859 phenylene bis(3-aminobenzoic acid) Ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate , bis(3-aminophenyl)isophthalate, hydrazine, Ν'-(1,4-phenylene)bis(4-aminobenzylbenzylamine), hydrazine, Ν'- (1, 3-(phenylene) bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzylamine), hydrazine, Ν'- (1, 3 —Extended phenyl) bis(3-aminobenzamide), hydrazine, Ν'-(4-aminophenyl)terephthalamide, hydrazine, Ν'-(3-aminophenyl) Para-xylyleneamine, hydrazine, Ν'-(4-aminophenyl)-isophenyl Formamide, hydrazine, Ν'-(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-double (4-amino group) Phenoxy)diphenylphosphonium, 2,2'-bis[4 mono(4-monoaminophenoxy)phenyl]propane, 2,2'-double [4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-double ( 3 —Amino-4-methylphenyl)hexafluoropropane, 2,2′-bis(4-aminophenyl)propane, 2,2′-bis(3-aminophenyl)propane, 2, 2'_bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3_bis(3-aminophenoxy)propane 1,4-bis(4-monophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexene Alkane, 1,7-bis(4-monoaminophenoxy)heptane, 1,7-bis (3) Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4- Aminophenoxy)decane, 1,9-32-200948859-bis(3-aminophenoxy)decane, l,l-bis(4-aminophenoxy)decane, 1, 1〇-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy) eleven Alkane, 1,12-bis(4-monophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, double (4 -Amino-3-methylcyclohexyl)methane, 1,3 -diaminopropane, 1,4 diaminobutane, 1,5-diaminopentane, 1,6-diamine Hexyl, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diamine Adecane, 1,12-diaminododecane, and the like. In addition, a diamine having a pendant group, a fluorine-containing substituent, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of the above may be exemplified as a diamine side chain, and specifically, may be exemplified. It is a diamine compound represented by the following formula [DA1] to formula [DA26].

[Chem. 14]

(In the formula [DA1] to the formula [DA5], R! is a group having a carbon number of 1 or more and 22 or a fluorine-containing alkyl group). -33- 200948859 [Chem. 15]

(In the formula [DA6] to the formula [DA9], R2 represents a COO-, - OCO-©, -CONH-, -NHCO-, -CH2-, - Ο-, -CO- or an NH-, and R3 represents carbon An alkyl group having 1 or more and 22 or less or a fluorine-containing alkyl group). [Chemistry 16]

(In the formula [DA10] to the formula [DA11], R4 represents a 0-, an OCH2-, -CH20-, a COOCH2- or -CH2OCO-, and R5 represents an alkyl group having 1 to 22 or less carbon atoms, an alkoxy group, Fluorinated alkyl or fluoroalkoxy). -34- 200948859 [Chem. 17]

(In the formula [DA12] to the formula [DA14], R6 represents a COO-,

-OCO-, a CONH-, an NHCO-, a COOCH2-, -ch2oco-, -CH20-, -〇CH2- or -CH2-, and R7 represents an alkyl group, an alkoxy group having a carbon number of 1 or more and 22 or less Fluoroalkyl or fluoroalkoxy). .

[Chem. 18]

(In the formula [DA15] to the formula [DA16], R8 represents a COO-, -0C0-, a CONH-, an NHCO-, a COOCH2-, a C Η 2 〇C 0 — , a C Η 2 〇 — _ 0 C Η 2 _ , _ C Η 2 I, _ 0 — or —ΝΗ—, R9 represents fluorine, cyano, trifluoromethyl, nitro, azo, indolyl, ethyl hydrazine, acetamidine Oxy or hydroxy). -35- 200948859 [Chem. 19]

[Chem. 20]

-36- 200948859 [Chem. 21]

In addition, a diamine oxirane represented by the following formula [DA27], etc., may also be exemplified. [Chem. 22] h2n-(ch2)3

Ch3 ίπ· -(CH2)3-NH2 [DA2 7] (in the formula [DA27], m is an integer of 1 to 10). ® Other diamine compounds may be used singly or in combination of two or more kinds depending on the characteristics of liquid crystal alignment, voltage maintenance characteristics, and accumulated electric charge when used as a liquid crystal alignment film. &lt;tetracarboxylic dianhydride&gt; The tetracarboxylic dianhydride used in the present invention is not particularly limited, and specific examples thereof are as follows. Pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, iota, 2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-tetracarboxylic acid-37- 200948859 dianhydride, 1,2,5,6-nonanedicarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylate Acid dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylate Acid dianhydride, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1 ,1,3,3,3—hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, double (3,4 _Dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3', 4, 4'_ Diphenylphosphonium tetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 1,3 -diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid Dihydride, oxydiphenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2 , 4,5 _cyclohexane tetracarboxylic dianhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl- 1,2,3,4-cyclobutane Carboxylic dianhydride, 1,3 - dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 2,3, 4,5_tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,4-dicarboxy-1, 2,3,4_tetrahydro-1 mononaphthalene succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]decane a 2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane —2,4,8,10_ Tetracarboxylic dianhydride, tricyclo[6·3·0.0&lt;2,6&gt;]undecane-3,5,9,11-tetracarboxylic dianhydride, 1,2 , 3,4-butane tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride Bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5--38-200948859 dioxotetrahydrofuranyl)-3-methyl —3 —cyclohexane-1,2-dicarboxylic dianhydride, tetracyclo[6,2,1,1 ,0,2,7]癸—4,5,9,10—tetracarboxylic dianhydride, 3,5,6-tricarboxycarboxyr-norbornane-2:3,5:6-dicarboxylic dianhydride, 1 , 2, 4, 5 - cyclohexane tetracarboxylic dianhydride, and the like. The tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the liquid crystal alignment property, voltage retention property, and accumulated electric charge when the liquid crystal alignment film is used. &lt;Copolymer&gt; The copolymer of the present invention is a polylysine obtained by reacting a diamine component of the diamine compound (A) and the diamine compound (B) with a tetracarboxylic dianhydride, and the poly Polyimine obtained by dehydration ring closure of proline. Any of these polyamic acids and polyimines is suitable as a copolymer for producing a liquid crystal alignment film. The liquid crystal alignment film obtained by using the copolymer of the present invention has a high voltage holding ratio when the content ratio of the specific diamine compound in the above diamine is φ, and can be early even when exposed to a high temperature for a long period of time. Relieves the residual charge accumulated by the DC voltage. Therefore, the content of the diamine compound (B) in the diamine component is preferably from 0.01 to 99 mol based on 1 mol of the diamine compound (A). More preferably from 0.1 to 50 moles, most preferably from 0.5 to 20 moles, particularly preferably from 0.5 to 1 moles of the reaction of the diamine component with the tetracarboxylic dianhydride to obtain the polyamine of the present invention. For the acid method, a conventional synthesis method can be used. It is usually a method of reacting tetracarboxylic acid-39-200948859 acid=anhydride with a diamine in an organic solvent. It is advantageous that the tetracarboxylic dianhydride and the diamine s should be relatively easy to carry out in an organic solvent without producing by-products. The organic solvent used in the reaction of the tetrabasic acid dianhydride and the diamine is not particularly limited as long as it can dissolve the produced polyamic acid. Specific examples thereof are listed below. Examples are N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, hydrazine-methyl caprolactam, dimethyl hydrazine, Tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, 7-butyrolactone 'isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone , methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellulolytic, methyl cellosolve acetate, ethyl cellosolve acetate , butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, Propylene glycol monomethyl ether, propylene glycol tert-butyl ether 'dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate single Methyl 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 A 3-methoxy butyl Acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl Ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane 'n-octane, diethyl ether, cyclohexanone, ethylene carbonate, Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, ethyl-40-200948859 acid propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-A Methyl oxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used singly or in combination. Further, even a solvent in which polylysine cannot be dissolved may be used in the above solvent in a range in which the produced polyamine acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyaminic acid, it is preferred that the organic solvent be dried by dehydration as much as possible. When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, for example, a solution obtained by stirring or dissolving a diamine component in an organic solvent, and directly adding a tetracarboxylic dianhydride, or making it a method of dispersing or dissolving in an organic solvent; and conversely adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent; and simultaneously adding tetracarboxylic dianhydride and two Any of these methods may be used as the method of the amine component. Further, when the tetracarboxylic dianhydride or the diamine component is composed of a plurality of kinds of compounds, it may be reacted in a state of being mixed beforehand, or may be individually reacted in order, or may be a mixture of low molecular weight bodies which are individually reacted. The reaction is carried out into a high molecular weight body. The polymerization temperature at this time may be selected from any temperature of from - 20 ° C to 150 ° C, but preferably from - 5 ° C to 1 ° C. In addition, the reaction can be carried out at any concentration, but it is difficult to obtain a copolymer of high molecular weight because the concentration is too low, and the viscosity of the reaction liquid is too high when the concentration is too high, so that uniform stirring becomes difficult -41 - 200948859 The total concentration in the reaction solution of the carboxylic acid dianhydride and the diamine component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added. In the polymerization of polyamic acid, the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably from 0.8 to 1.2. As with the general polycondensation reaction, the molecular weight of the polyamic acid formed by the molar ratio approaching 1.0 is the largest. The polyimine of the present invention is a polyimine obtained by subjecting the above polyamic acid to dehydration ring closure, and can be used as a polymer for obtaining the liquid crystal alignment film. The polyamidene of the present invention, proline is used. The dehydration ring closure ratio (醯 imidization ratio) of the base is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose or purpose. The method of imidating polyruthenium imidate is exemplified by hot amination of a solution of polylysine directly by heating, and the catalyst is added to a solution of polylysine to imidize. The temperature at which the hydrazide imidization reaction is carried out is carried out at a temperature of from 100 ° C to 400 ° C, preferably from 120 ° C to 250 °, and preferably at the same time Outside the system. The ruthenium imidization of polylysine may be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles of the guanyl group, preferably 2 to 20 moles, and the amount of the anhydride is 1 to 5 moles of the amidate group, preferably 3 Up to 30 moles. As the inert catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like can be exemplified, wherein pyridine is maintained from -42 to 200948859 to maintain moderate alkalinity for the reaction to proceed. good. The acid anhydride may, for example, be acetic anhydride, trimellitic anhydride or benzene tetracarboxylic anhydride. In the case where an acid anhydride is used, purification after completion of the reaction becomes easy and preferable. The imidization ratio of the ruthenium imidized by the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. In the case where the resulting polyamic acid or polyimine is recovered from a reaction solution of polyglycolic acid or polyimine, the reaction solution can be poured into a weak solvent to form a precipitate. The weak solvent used for the precipitation may, for example, be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water or the like. Pour into the weak solvent and the polymer of the sinking chamber is filtered and returned to dryness at normal temperature or under normal pressure or reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. The weak solvent at this time is, for example, an alcohol, a ketone, a hydrocarbon or the like. When three or more kinds of weak solvents selected from the above are used, it is preferable to further improve the purification efficiency. The molecular weight of the poly-proline and the polyimine contained in the liquid crystal alignment treatment agent of the present invention is determined by considering the strength of the coating film obtained therefrom and the workability at the time of formation of the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the GPC (gel permeation chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000. &lt;Liquid Crystal Alignment Treatment Agent&gt; The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and is a solution obtained by dissolving a resin component for forming a resin film in an organic solvent -43-200948859 . Here, the above resin component is a resin component containing at least one polymer selected from the above polymers of the present invention. In this case, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, most preferably from 3 to 10% by mass. In the present invention, the above-mentioned resin components may all be the copolymer used in the present invention, and other polymers other than the polymer of the present invention may be mixed. At this time, the content of the polymer other than the polymer of the present invention in the resin component is from 5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass. The other polymer, for example, a diamine component which can be reacted with a tetracarboxylic dianhydride, can be obtained by using a diamine compound (A) and a diamine compound other than the diamine compound (B). Imine and the like. The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent which can dissolve the above resin component. Specific examples thereof are listed below. Examples are hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl milling, hexamethyl sulfoxide, γ-butyrolactone, 1,3 Dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate Ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used singly or in combination. 〇 份 表 成 成 成 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 m m m m m m m m m m m m m m m m m m m m m m m m m m m Examples thereof -44 - 200948859 A solvent or a compound which is smooth, a compound which improves the adhesion between a liquid crystal alignment film and a substrate, and the like. Examples of the solvent (weak solvent) for improving film thickness uniformity or surface smoothness are as follows. Examples are, 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 monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, two Propylene glycol monoacetate 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-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether , diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether 'dihexyl ether, 1-hexanol, n-hexane, n-pentyl Alkane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 - methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-A Propyl oxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1_phenoxy-2-propanol, propylene glycol monoethyl-45- 200948859 acid ester, propylene glycol diacetate, propylene glycol-1_monomethyl ether-2 acetic acid vinegar, propylene glycol_1 monoethyl acid 2--acetic acid vinegar, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. with low surface tension Solvents, etc. These weak solvents may be used singly or in combination of plural kinds. When the solvent is as described above, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass based on the total of the solvent contained in the liquid crystal alignment agent. Examples of the compound which improves post-film uniformity or surface smoothness are fluorine-based surfactants, rhodium-based surfactants, nonionic surfactants, and the like. More specifically, for example, F TOP EF301, EF3 03, EF352 (manufactured by TOKEMU PRODUCT), MEGAFAX F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), FLU0RAD FC430, FC431 (manufactured by Sumitomo 3M), ASAHIGUARD AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SCI 05, SCI 06 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate are the functional decane-containing compound or the epoxy group-containing compound shown below. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyl-46-200948859 triethoxy Basear, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-alkylaminotrimethoxydecane, N-ethoxycarbonyl-3 Aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 1〇-trimethoxydecane 1,1,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diaza Mercaptoacetate, 9-triethoxydecyl- 3,6-diazepine acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3 -Aminopropyltriethoxydecane, N-phenyl-3-ylaminopropyltrimethoxydecane, N_phenyl-3 Aminopropyltriethoxydecane, N-bis(oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxy Base decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6 _ hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4 - hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamine oxime methyl)cyclohexane, Ν, Ν, Ν ', Ν 'four-glycidyl- 4,4'-diaminodiphenylmethane and the like. When the compound which improves the adhesion to the substrate is used, the amount thereof is preferably from 10,000 parts by mass to about 30 parts by mass of the resin component contained in the liquid crystal alignment agent, preferably from 1 to 1. 20 parts by mass. When the amount of use is less than the mass part, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the liquid crystal alignment property may be deteriorated. In addition to the above, the liquid crystal alignment treatment agent of the present invention may be added to the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, without impairing the effects of the present invention. The electric or conductive material 'and further' may be added as a crosslinkable compound for the purpose of increasing the hardness or density of the film when it is a liquid crystal alignment film. &lt;Liquid Crystal Alignment Film, Liquid Crystal Display Element&gt; The liquid crystal alignment treatment agent of the present invention is applied onto a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, or unaligned treatment such as vertical alignment use. Can be used as a liquid crystal alignment film. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. Further, from the viewpoint of simplification of the process, it is preferable to use a substrate which forms an ITO electrode or the like which is useful for driving a liquid crystal. Further, it is also possible to use an opaque material such as a tantalum wafer which is a single-sided substrate of the reflective liquid crystal display element, and a material such as aluminum which can reflect light can be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is generally a method of screen printing, lithography, flexographic printing, ink jet printing or the like. As for other coating methods, there are dip coating, roll coating, slit coating, spin coating, etc., and these may be used depending on the purpose. After the liquid crystal alignment treatment agent is applied onto the substrate, the firing can be carried out by heating a heating mechanism such as a -48-200948859 hot plate at 50 to 300 ° C, preferably 80 to 25 (TC) to evaporate the solvent. The coating film is formed. The thickness of the coating film formed after firing is too low for the power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 10 nm. When the liquid crystal is aligned horizontally or obliquely, the film after firing is treated by rubbing or polarized ultraviolet light irradiation, etc. The liquid crystal display element of the present invention is self-assisted by the above method. In the liquid crystal alignment film obtained by the invention, a liquid crystal cell is produced by a conventional method, and a liquid crystal cell is produced as a liquid crystal display element. As an example of the liquid crystal cell production, a liquid crystal alignment is prepared. One of the films is a pair of substrates, and the spacer is dispersed on the liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface becomes the inner side, the other substrate is bonded, the liquid crystal is decompressed and packaged, or The method of laminating the liquid crystal on the liquid crystal alignment film surface of the cloth spacer, laminating the substrate, and encapsulating the film, etc. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμιη. As above, the liquid crystal of the present invention is used. The liquid crystal display element produced by the alignment treatment agent is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail, but the present invention The explanation is not limited by the examples. -49- 200948859 [Synthesis of diamine compound] <Synthesis Example 1> Synthesis of diamine compound (4)

A solution of the compound (2) (29.92 g '277 mmol) and triethylamine (28_03 g, 277 mmol) in tetrahydrofuran (300 g) was cooled to 10. (: In the following, a solution of the compound (1) (60·76 g, 263 mmol) in tetrahydrofuran (150 g) was added dropwise while paying attention to the heat. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C. The reaction was continued. After confirming the completion of the reaction by HPLC (high-speed liquid chromatography), the reaction liquid was poured into distilled water (2 liters), and the precipitated solid was filtered and washed with ethanol (450 g) to obtain a compound. (3) (yield: 72.91 g, yield: 92%). 1H-NMR (400 MHz &gt; DMSO-d6 » δ ppm) : 9.79 (1Η, t) , 9· 10-9.09 ( 2Η,m ) &gt ; 9.00-8.96 ( 1 Η &gt; m ) ' 8.61 (1Η, broad) , 8.50-8.48 ( 1H' m) ' 7.79-7.76 ( 1H' m -50- 200948859 )' 7.40-7.36 (lH,m) , 4.57 (2H, s). Then 'in the presence of hydrogen, compound (3) (72.00 g '238 mmol), 5% palladium/carbon (aqueous form, 7.2 g, 10 wt ° / 搅拌) at 60 r And a mixture of 1,4 -dioxane (720 g). After the reaction was completed, the catalyst was filtered with celite, and the solvent was evaporated to give a crude product. Wash the product dispersion, to obtain the diamine compound (4) (yield: 43.62 g, yield: 76%).

1H-NMR (400MHz, DMSO-d6, &lt;5 ppm): 8.64 (1H, t) &gt; 8.50 ( 1H &gt; d ) , 8.44 (lH, d) * 7.67 ( 1H &gt; d ) , 7.34 (lH) , q) , 6.23 (2H, d), 5.94 (lH, s) &gt; 4.87 (4H &gt; s ) , 4.3 9 ( 2H, d ). &lt;Synthesis Example 2&gt; Synthesis of diamine compound (7)

A solution containing compound (5) (40.00 g, 328 mmol) and triethylamine (33.18 g, 328 mmol) in tetrahydrofuran (400 g) was cooled -51 - 200948859 to below 10 °C, with a fever A solution of the compound (1) (72.00 g, 312 mmol) in tetrahydrofuran (176 g) was added dropwise. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was continued. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (3.5 liters), and the precipitated solid was filtered, washed with water, and then washed with methanol (200 g) to obtain compound (6) (yield: 81.4 g, yield) Rate: 82%). 1H-NMR (400MHz &gt; DMSO-d6 &gt; δ ppm) : 8.83-8.34 (5H, m) &gt; 7.83 -7.66 ( 1 H &gt; m ) , 7 · 3 9 - 7 · 3 3 ( 1 H, m ) &gt; 4.69-4.49 ( 2H - m ) , 2 · 9 1 - 2.8 5 ( 3 H,m ). Next, compound (6) (80.00 g, 253 mmol), palladium hydroxide/carbon (aqueous form, 8.0 g, 10 wt%) and 1,4-dioxin were stirred at 23 ° C in the presence of hydrogen. A mixture of alkanes (1200 g). After the completion of the reaction, the catalyst was filtered through celite, and the solvent was distilled off on a rotary evaporator to give a crude product. The obtained crude product was uniformly dissolved in tetrahydrofuran (150 g), and the solution was added dropwise to hexane (660 g) at -20 ° C to precipitate a solid. Subsequently, it was filtered and washed with cold hexane to obtain a diamine compound (7) (yield: 7 4 · 9 8 g, yield: 98%). 1H-NMR (400MHz &gt; DMSO-d6 &gt; δ ppm) : 8.46-8.34 (2H ' m) 5 7.63-7.54 ( 1 H &gt; broad ) , 7.3 6 - 7 · 3 3 ( 1 H, m ), 5.86-5.76 ( 3H,m ) , 4.86 ( 4H,s) , 4.5 7-4.5 3 ( 2H,broad) ' 2.8〇 ( 3H, broad). &lt;Synthesis Example 3&gt; Synthesis of diamine compound (10) -52- 200948859 [Chem. 16]

(8) 冷却 Cool a solution containing compound (8) (16.69 g '137 mmol) and triethylamine (13.82 g, 137 mmol) in tetrahydrofuran (200 g) to below 10 °C, and pay attention to heat A solution of the compound (1) (30.00 g, 130 mmol) in tetrahydrofuran (150 g) was added dropwise. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C to continue the reaction. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (2.8 liters), and the precipitated solid was filtered, washed with ethanol (200 g), and the compound (9) was obtained (yield: 34.53 g, Yield: 84%). 1H-NMR (400MHz &gt; DMSO-d6 » δ ppm) : 9.30 ( 1H , t ) , 9.01-9.00 ( 2H,m ) &gt; 8.95 -8.93 ( 1 H * m ) &gt; 8.47

(lH, d) , 8.42 (lH, dd), 7.69 (2H, d) * 7.32 ( 1H , q ) , 3.64 - 3.58 ( 2H, m ) , 2.92 ( 2H, t ). Next, the compound (9) (32.00 g, 101 mmol), 5% palladium/carbon (aqueous form, 3.2 g, 1 (^1%) and 1, 4 in the presence of hydrogen were stirred at 60 °C. a mixture of dioxane (32 g). After the end of the reaction, the product was obtained by distilling off the solvent with a rotary evaporator, and then the solvent was evaporated to give a crude product of -53-200948859. Disperse and wash with tetrahydrofuran (150 g) The net crude product was obtained to give the diamine compound (10) (yield: 19.21 g, yield: 74%) ° 1H-NMR (400 MHz, DMS0-d6, δ ppm): 8.43-8.39

(2H,m), 8.09 ( 1H ' t) ' 7.63 ( 1H,d), 7.30 ( 1H ,dd ) , 6.16 ( 2H,d) , 5.92 ( 1H ' d ) ,4.84 ( 4H ' s ),3.44- 3.28 ( 3H,m ) , 2.82 ( 3H,t). &lt;Synthesis Example 4&gt; Synthesis of diamine compound (14) [Chem. 17]

(12) 滴 In a solution containing compound (12) (35.00 g, 321 mmol) and triethylamine (97.39 g, 962 mmol) in tetrahydrofuran (24 g), compound (11) (29.84) A solution of 160 mils of tetrahydrofuran (60 g). After completion of the dropwise addition, the reaction was followed by HPLC, and after confirming completion of the reaction, dichloromethane (1 liter) was added, and then washed with distilled water (600 ml) three times. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was filtered and evaporated to give the crude product of compound (13). The obtained crude product was recrystallized from ethyl acetate (-54-200948859 550 g) /hexane (1 liter) to give compound (13) (yield: 38.74 g, yield: 88%). 1H-NMR (400MHz &gt; CDC13 &gt; δ ppm) : 8.79 ( 1H,d ), 8.71 ( 1H,d) , 8.66 ( 1H,dd ) ,8.46 ( 1H « dd ) &gt; 7.8 8-7.85 ( 1 H &gt; m ) , 7.40 ( 1H, q) , 7.30 ( 1H, d) , 5.38 ( 2H, s ). Next, compound (13) (20.00 g, 72.7 mmol), platinum (IV) oxide (aqueous form, 2.0 g, 10 wt%) and ethyl acetate/ethanol (200) were stirred at 40 ° C in the presence of hydrogen. a mixture of grams, 1 00/50 (v/v%)). After completion of the reaction, the catalyst was filtered through diatomaceous earth, and then the solvent was distilled off by a rotary evaporator to obtain a crude product of compound (14). The obtained crude product was purified by silica gel column chromatography (solvent solvent hexane/ethyl acetate (1 0 0/5 0 v/v%)) to give the diamine compound (14) (yield: 15.27 g, yield: 98%). 1H-NMR (400MHz, CDC13, 5 ppm): 8.66 ( 1H,d )&gt; 8.57 ( 1H &gt; dd ) , 7.7 7 - 7.7 3 ( 1 H,m ) , 7.3 3-7.29 ( lH,m) , 6.67 (lH, d), 5.00 (2H, s), 3.37 (4H, s &lt; Synthesis Example 5 &gt; Synthesis of diamine compound (16) -55- 200948859 [Chem. 18]

(2)

(16) Add in a mixture of compound (2) (29.98 g, 277 mmol) ❿, sodium bicarbonate (29.12 g, 347 mmol) and distilled water (630 g) at 23 °C. A solution of compound (11) (43.0 g, 231 mmol) in ethanol (830 g). After completion of the dropwise addition, after confirming completion of the reaction by HPLC, dichloromethane (2 L) was added to remove the aqueous layer. Subsequently, the organic layer was washed three times with saturated brine (500 ml), and the organic layer was dried over anhydrous magnesium sulfate. The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 liter) to yield Compound (15) (yield: 55.28 g, yield: 87%). ❹ 1H-NMR (400MHz &gt; CDC13 &gt; δ ppm) : 9.18 ( 1H,d )&gt; 9.17 ( 1H &gt; broad) » 8.66-8.62 ( 2H &gt; m) &gt; 8.29-8.25 (1H,m) , 7.69-7.66 ( 1 H,m ) , 7.3 7 - 7 · 3 3 ( 1 H,m ) &gt; 6.90 ( 1H &gt; d ) , 4.68 (2H, m). Then, the compound (15) (3.0 g '10.9 mmol), lead (IV) (aqueous form, 0.3 g, 10 wt%) and 1,4-dioxane were stirred at 23 ° C in the presence of hydrogen. a mixture of (30 grams). After the completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off on a rotary evaporator to obtain a diamined- 56- 200948859 compound (16) (yield: 2.30 g, yield: 98%). 1H-NMR (400MHz, CDC13, δ ppm) : 8.63 ( 1H &gt; d ), 8.52 ( 1H, dd ) , 7 · 7 1 - 7.6 6 ( 1 H, m ) , 7.28-7.24 ( lH,m) , 6.53 (lH, d), 6.18-6.11 (2H, m), 4.22 (2H, s), 3.70 (1H, s), 3.5 6 - 3 · 3 4 ( 4 H, br o ad ). &lt;Synthesis Example 6&gt; Synthesis of diamine compound (19) [Chem. 19]

(2)

Containing compound (17) (50.00 g, 170 mmol), potassium carbonate (47.01 g, 340 mmol), copper iodide (I) (6.48 g '34.0 mmol), N at 40 °C Compound (2) (36.78 g, 340 mmol) was added dropwise to a mixed solution of methylglycine (6.06 g, 68.0 mmol) and DMSO (dimethyl sulfonium) (1 L). After completion of the dropwise addition, after confirming the completion of the reaction by HP LC, ethyl acetate (4 L) / distilled water (5 L) was added, and insoluble materials were removed by filtration. Subsequently, the aqueous layer was removed twice by extraction from ethyl acetate (500 g) and the organic layer was combined and dried over anhydrous magnesium sulfate - 57 - 200948859. After distilling off the solvent by a rotary evaporator, ethyl acetate (700 ml) / hexane (2 liter) was recrystallized to give compound (18) (yield: 23.04 g, yield: 49%). 1H-NMR (400MHz, CDC13, &lt;5 ppm): 8.63 ( 1 Η &gt; broad ) , 8.5 0- 8.49 ( 1 H &gt; broad ) , 7.95 ( 1H, t), 7.80-7.76 ( 3H, m) , 7.67 ( 1H, t) , 7.39 ( 1H, q), 4.52 ( 2H, d ). Next, compound (18) (1.0 g, 3.65 mmol), lead (IV) oxide (aqueous form, 0.1 g, 10 wt%) and methanol (10 g) were stirred at 23 ° C in the presence of hydrogen. mixture. After the completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off on a rotary evaporator to obtain a diamine compound (19) (yield: 0.97 g, yield: 97%).

1H-NMR (400MHz, DMSO-d6, δ ppm) : 8.52 ( 1H , d ) , 8.41 (lH, dd) , 7.69 (lH, d) , 7.32 (lH, q ), 5.60 ( 1H, t) , 5.17 (2H, s), 4.37-4.14 (4H &gt; m &lt; Synthesis Example 7 &gt; Synthesis of diamine compound (23) -58- 200948859 [Chem. 20]

(21) 维持 Maintain a solution of compound (21) (51.43 g '281 mmol) of tetrahydrofuran (300 g) under 1 〇t: under nitrogen atmosphere, and add the compound while paying attention to heat ( 20) (50.00 g, 281 mmol), triethylamine (170.5 g, 1.69 mmol) and DMAP (4-dimethylaminopyridine) (6.87 g, 56.2 mmol) of tetrahydrofuran (500 g) Solution. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the mixture was stirred for 1 hour, and then heated to reflux. After confirming the completion of the reaction by HPLC, the reaction hydrazine liquid was poured into distilled water (6.4 liter), filtered, and washed with water to obtain a crude product. The crude product was recrystallized from tetrahydrofuran (243 g) / hexane (1458 g) to yield Compound (22) (yield: 72.58 g, yield: 8 9%). 1H-NMR (400 MHz &gt; DMSO-d6 &lt; 5 ppm): 11.25 (1H, s), 9.18 (1H, d), 9.09 (2H, dd), 8.82 (lH, dd), 8.57 (lH, t) &gt; 8.3 8-8.3 5 ( 1 H » m ) &gt; 7.64 ( 1H &gt; q )0 Then 'in the presence of hydrogen, the compound (22 ) is stirred at 90 ° C ( -59- 200948859 20.00 g, A mixture of 69.4 mmol, 5% palladium-carbon (10 wt%) and 1,4-dioxane (400 g) was filtered with diatomaceous earth to rotate the evaporator product. The obtained crude compound (23) was washed with ethanol (75 g) (yield: 10.14 g) yield: 1H-NMR (400 MHz, DMSO-d6, &lt;5, s) &gt; 9.03-9.01 (1H &gt; m ), 8.72-5 8.23-8.19 (1H, m), 7.54-7.50 (1H, 2H, m), 5·63-5·61 (1H, m) &gt; 4.75-^ &lt;Synthesis Example 8&gt; Synthesis of diamine compound (26) Aqueous form, 2.0 g of a compound. After completion of the reaction, the solvent was distilled off to give a crude product to give a diamine (4%). Ppm ) : 9.87 ( 1H ? .70 ( 1Η &gt; m ), m) &gt; 6.27-6.26 ( ^.73 ( 2H &gt; m ).

(26) A solution containing the compound (21) Mohr in tetrahydrofuran (120 g) was cooled while under nitrogen atmosphere. The compound (24) molar and triethylamine (68.18 g '674 m) were added dropwise while heating. Mohr-60- (20.00 g, 112 mM but below 1 〇 °c, and (20.57 g, 112 mM) & DMAP (2.74 * 200948859, 22.5 mmol) tetrahydrofuran (200 g) solution. The reaction temperature was raised to 23 ° C, and after stirring for 1 hour, the mixture was further refluxed for 17 hours. After confirming the completion of the reaction by HPLC, the reaction liquid was distilled (2.6 liter), filtered, and washed with water to obtain crude ethanol (40 g). The obtained crude product was dispersed and washed, and then dried to obtain Compound (25) (yield: 16.45 g, yield: 1H-NMR (400 MHz, DMSO-d6, &lt;5 ppm): , s) - 9.15 -9.14 ( 1Η &gt; m ) &gt; 8.86 ( 1Η &gt; d ), ,d) - 8.64-8.60 ( 1 H · m ) &gt; 8.33 ( 1H &gt; d ), ,d) , 7.66(lH,q ), 2.92 ( 2H, t ). Next, a mixture of 15.00 g of the compound, 52.0 mmol, 5% palladium on carbon (aqueous form, 10 wt%) and 1,4-dioxane (150 g) was stirred at 60 ° C in the presence of hydrogen. Instead, after filtering the catalyst with diatomaceous earth, the crude product of the solvent (26) was distilled off by a rotary evaporator. The crude product was purified by purifying the hexane/ethyl acetate (1 〇〇/5 〇v/v%) from a solvent column, and then recrystallized from hydrogenfuran (400 g) / hexane (600 g). (26) (yield: 6.11 g, yield: 51%). 1H-NMR (400MHz, DMSO-d6, &lt;5 ppm): , s), 9.10 (1H, d), 8.72 (1H, dd), 8.30-, m), 7.90 (1H, s) &gt; 7.52 ( 1H &gt; q ) &gt; 6.75 ( , 6.61 ( 1H, d) , 5.99 ( 1H, m) , 4.65 - 4.59 (after the end of the addition, heat the body and pour the steamed product into a furnace, dry 5 1%). 11-4 ( 1 Η 8.77 ( 1 Η 8.06 ( 1 Η (25 ) ( 1.5 g, should be prepared after the completion of the chromatography (dissolved from the four-made diamine 9-54 (in 8.27 (in 1 Η, d) 4H &gt ; m ) -61 - 200948859 &lt;Synthesis Example 9&gt; Synthesis of diamine compound (29) [Chem. 22]

(29) Slowly add the compound to a solution of compound (27) (10.00 g '49.0 mmol) and triethylamine (59.50 g, 588 mmol) in tetrahydrofuran (1 g) under nitrogen atmosphere. (12) (21.39 g '196 mmol). After completion of the reaction, the reaction liquid was poured into distilled water (1 liter), filtered, and washed to obtain a crude product of the compound (28). The crude product obtained was recrystallized from acetonitrile (200 g) / ethyl acetate (30 g) to yield compound (2 8 ) (yield: 1 1 · 3 5 g, yield: 61%). 1H-NMR (400MHz, DMSO-d6, δ ppm ) : 8.74-8.73

(3H,m) ' 8.61 ( 2H,dd) , 7.93 ( 2H,d) , 7.50 ( 2H ,q ) , 7_44 ( 1H,s ) , 5.56 ( 4H,s ). Then, the compound (28) (-62-200948859 8.00 g, 20.1 mmol), platinum (IV) (aqueous form, 0.8 g, 10 wt%) and 1,4 were stirred at 60 ° C in the presence of hydrogen. a mixture of dioxane (80 g). After the completion of the reaction, the catalyst was filtered through celite, and the obtained crude product was evaporated to dryness eluted with EtOAc (EtOAc) (Yield: 4.66 g, yield: 7 2%).

1H-NMR (400MHz, DMSO-d6, δ ppm) : 8.65 ( 2H ,d ) , 8.52 ( 2H &gt; dd ) , 7 · 8 8 - 7 · 8 5 ( 2 H,m ) , 7.40 ( 2H,q ), 6.68 (lH, s), 6.07 (lH, s), 4.96 (4H, s) &gt; 4.25 ( 4H &gt; s ) ° &lt;Synthesis Example 1 〇&gt; Synthesis of diamine compound (34) twenty three]

-63- 200948859 A mixture of compound (31) (81.60 g, 74.1 mmol), potassium hydroxide (18.29 g '24.7 mmol) and 〇1^180 (375 g) was heated to a nitrogen atmosphere. After 50 ° C, a solution of compound (30) (50.00 g, 24.7 mmol) in DMSO (125 g) was added dropwise. After completion of the dropwise addition, the reaction liquid was poured into 5 mass% hydrochloric acid ice water (4 liters), and the solid was filtered and washed with water to obtain a wet product of the compound (32). Subsequently, recrystallization was carried out with 2-propanol (205 g) / hexane (335 g) to give Compound (32) (yield: 49·0 g, yield: 72%).

1H-NMR (400MHz, DMSO-d6, δ ppm) : 9.73 ( 1H

, s) , 8_86 (lH, d) , 8_42 (lH, dd) &gt; 7.1 1 -7.05 ( 3H , m ) , 6.90-6.87 ( 2H, m ). Next, a solution of the compound (21) (19.34 g, 109 mmol) in tetrahydrofuran (180 g) was cooled to below 10 ° C under a nitrogen atmosphere, and the compound (31) was added dropwise while paying attention to heat generation (30.0). Gram, 109 mM) Triethylamine (33.0 g, 324 mmol) and DMAP ( 2.65 g, 21.7 mmol) in DM SO (300 g). After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the mixture was stirred for 1 hour, and then heated and refluxed for further 19 hours. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (3.9 liter), filtered, washed with water, and washed with methanol to give a crude product. After the obtained crude product was dissolved in chloroform, the insoluble matter was filtered. Subsequently, the filtrate was concentrated, and purified by a silica gel column chromatography (solvent solvent: 1,2-dichloroethane / ethyl acetate (100 / 4 〇 ν / ν%)) to obtain compound (33) (yield: 35.8 g, yield: 86%). 200948859 1H-NMR (400MHz &gt; DMSO-d6 &gt;&lt;5 ppm) , dd ) , 8.92 - 8.91 ( 2H, m ) , 8.52 - 8.48 ( 7.69 - 7.66 ( 1 H, m ) , 7.53 - 7.51 ( 2H ) , m), 2H, m ) , 7.24 ( 1 H, d ). Then, under a nitrogen atmosphere, a solution containing the compound (33, 78.7 mmol) and iron powder (26.36 g, 472 mmol: 170 g) was heated to 70 ° C, and then 10 masses of 12.63 g '236 m were added dropwise. An aqueous solution of Moh. After the reaction was over, the solid was filtered. Subsequently, after the aqueous layer was removed from the filtrate, a crude product was obtained by rotating the organic layer. Next, the obtained crude acid-producing ethyl ester (1 liter) was washed with distilled water (500 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated to give the compound (34) as methanol-propanol (100 g). The crude product was prepared to give the diamine compound (34) (yield: 15.4 g, 〇1H-NMR (400 MHz, DMSO-d6, δ ppm) ' dd ) ' 8.85 ( 1H, dd ) , 8.43 - 8.40 ( 1 H - 7.59 ( 1H &gt; m ) , 7.19-7.16 (2H, m) ^ 6.88- m) , 6.53 (lH, d) , 6.02 (lH, d) . 5.8 1 ' 4.69 ( 2H, s ) &gt; 4.57 ( 2H &gt; s ). &lt;Synthesis Example 1 1&gt; Synthesis of diamine compound (37): 9.29 (1H 2H, m ) &gt; 7.44 - 7.40 ( ) (30.00 g) of toluene (% ammonium chloride (concentrated by diatomaceous earth evaporator) After dissolved in B three times, there is (100 g)/2 product recrystallization i rate: 6 1 %): 9.20 (1H m) 5 7.62- .6.84 ( 2H, (1 Η, dd ) -65- 200948859 twenty four]

The compound (32) (1,700 g, 61.6 mmol), the compound (35) (6.57 ml, 67.7 mmol) and triphenylphosphine (20.99 g, 80.0 mmol) were placed in an ice bath under a nitrogen atmosphere. The tetrahydrofuran (340 g) solution was cooled, and a solution containing DEAD (diethyl azodicarboxylate) (40% by mass in toluene, 34.84 ml, 80.0 mmol) was slowly added dropwise. After the completion of the dropwise addition, the reaction was slowly raised to 23 ° C to carry out a reaction. After confirming the completion of the reaction by HPLC, the solvent was distilled off with an evaporator to obtain a crude product. Subsequently, recrystallization was carried out twice with 2-propanol (45 g) to give Compound (36) (yield: 17.77 g, yield: 79%). 1H-NMR (400MHz, CDC13, &lt;5 ppm): 8.84 (1H,d), 8.71 (1Η &gt; broad ) , 8.63 ( 1Η,dd ) , 8 3〇( ih, dd ) , 7.80 (lH,d ), 7.36(lH,q) , 7.12_7〇8(4H, m ) , 7.01 ( 1H,d ) , 5.04 ( 2H,s ). Next, the compound (36) (15.00 g, 40-8 mmol) and the oxidation pin (11^) (-66 - 200948859 water-containing form, 1.5 g, 10 wt%) were scrambled under a nitrogen atmosphere in the presence of hydrogen at 23 °. %) and a mixture of 1,4-dioxane (230 g). After completion of the reaction, the catalyst was filtered through diatomaceous earth, and then the solvent was distilled off on a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized from 2-propanol (60 g) to give diamine compound (37) (yield: 9.66 g, yield: 7 7%). 1H-NMR (400MHz, CDC13, 5 ppm): 8.66 (1H &gt; d ), 8.57 (lH, dd), 7.77 (lH, m), 7.3 4 (lH,q), 6.87 ( 4H &gt; s ) &gt 6.69 ( 1H &gt; d ) &gt; 6.16 ( 1H &gt; d ) , 6.07( 1H ' dd) ' 5.02 ( 2H, s) , 3.65-3.48 ( 4H, broad). &lt;Synthesis Example 12&gt; Synthesis of diamine compound (4〇)

Cool the solution containing the compound (3 8 ) ( 23.45 g, 190 mmol) and triethylamine (19.23 g '277 mmol) in tetrahydrofuran (23 g) to below 10 °C. A solution of the compound (1) (41.68 g, 180 Torr) in tetrahydrofuran (11 g) was added dropwise. After the dropwise addition -67- 200948859, the reaction temperature was raised to 23 ° C and the reaction was carried out. After confirming the completion of the reaction by HPLC (high-speed liquid chromatography), the reaction liquid was poured into distilled water (1.5 liter), and the precipitated solid was filtered and washed with water. Subsequently, the solid was washed with ethanol (380 g) to obtain Compound (39) (yield: 50.82 g, yield: 89%).

1H-NMR (400MHz, DMS〇-d6, 6 ppm): 9.76 ( 1H , t) , 9.09-9.02 ( 2H, m ) , 8 · 9 9 - 8.9 3 ( 1 H ' m ) ' 8.50 (1H, mbroad &gt; 7.64-7.60 ( 1H 1 m ) &gt; 7.3 6-7.3 2 ( 1 H &gt; m ) , 7.20-7.14 (lH,m) , 4.57(2H,s) , 3.35(2H, s ) ° The compound (39) (48.00 g, 151 mmol), 5% palladium/carbon (aqueous form, 4.8 g, 10 wt%) and 1,4-dioxane were stirred at 60 ° C in the presence of hydrogen. a mixture of 490 g). After completion of the reaction, the catalyst was filtered with diatomaceous earth, and the solvent was distilled off on a rotary evaporator to give a crude product. The obtained crude product was washed with ethanol (300 g) to give a diamine compound (40) (yield: 27.20 g, yield: 70%).

1H-NMR (400MHz, DMSO-d6, δ ppm): 8.64 (1H, t), 8.50 (lH, d), 8.44 (lH, d), 7.67 (lH, d), 7.34 (1H, q), 6.23 ( 2H,d) , 5.94 ( 1H,s) 4.87 ( 4H,s ) , 4.39 ( 2H,d ). &lt;Synthesis Example 13&gt; Synthesis of diamine compound (43) -68 .200948859 [Chem. 26]

(41)

(43) 冷却 Cool the solution containing the compound (41) (15.22 g, 142 mmol) and triethylamine hydrazine (15.09 g, 149 mmol) in tetrahydrofuran (150 g) to below 10 °C. A solution of the compound (1) (31.1 g, 135 mmol) in tetrahydrofuran (50 g) was added dropwise while heating. After the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (1 liter), and the precipitated solid was filtered and washed with water. Subsequently, the solid was washed with ethanol (300 g) to obtain a compound (42) (yield: 36.92 g, yield: 90%). 1H-NMR (400 MHz &gt; DMSO-d6 &gt; δ ppm) : 9.75 (1Η, broad), 9.10 ( 2H, s) , 8.97-8.92 ( 1 H &gt; m ) - 7.40- 7·22 ( 5H, m) , 4.5 9 - 4.5 2 ( 2 H, m ). Next, compound (42) (36.00 g, 119 mmol), 5% palladium/carbon (aqueous form, 3.6 g, 10 wt%) and 1,4-dioxane were stirred at 60 ° C in the presence of hydrogen. a mixture of (300 g). After completion of the reaction, the catalyst was filtered with diatomaceous earth, and then the solvent was distilled off on a rotary evaporator to yield crude product -69-200948859. The obtained crude product was recrystallized from methanol (200 g) to give the diamine compound (4 3 ) (yield: 21.5 g, yield: 72%).

1H-NMR (400MHz, DMSO-d6, δ ppm): 8.55 ( 1H , broad ) , 7.34 - 7.17 ( 5H &gt; m ) &gt; 6.28 ( 2H &gt; s) &gt; 6.98- 6.94 ( 1H,m) 1 4.85-4.74 ( 4H 1 broad) » 4.42-4.35 ( 2H,m ). Table 4] Diamine hydrazide i x x x X X η Synthesis Example 1 4 -CONH-methylene single bond pyridyl ring 1 Synthesis Example 2 7 —con(ch3)—methylene single bond pyridyl ring 1 Synthesis Example 3 10 -CONH-extended ethyl single bond pyridyl ring 1 Synthesis Example 4 14 -0-methylene single bond pyridine ring 1 Synthesis Example 5 16 -NH-methylene single bond pyridyl ring 1 Synthesis Example 6 19 -NH - Methylene single bond pyridine ring 1 Synthesis Example 7 23 -NHCO- Single bond single bond pyridine ring 1 Synthesis Example 8 26 -NHCO- Single bond single bond pyridine ring 1 Synthesis Example 9 29 - 0 - Methylene single bond pyridine Ring 2 Synthesis Example 10 24 —0 — Phenyl-OCO-pyridine ring 1 1 Synthesis Example Π 37 —0—Phenyl-och2-mouth ratio steep ring•-------- 1 Synthesis Example 1 40 -coo - Ethylethyl single-chain pyrrole ring 1 Synthesis Example 2 43 -CONH-methylene single bond lysine 1 [Synthesis of polyimine] The following is abbreviated as a compound such as tetracarboxylic dianhydride used. (tetracarboxylic dianhydride) CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride-70- 200948859 BODA :bicyclo[3,3,0]octane-2,4,6,8_ Tetracarboxylic dianhydride [Chem. 36] (Diamine) DBA: 3,5-Diaminobenzoic acid p-PDA: p-phenylenediamine PCH7DAB : 1,3 -diamino _ 4 -[4_ (trans —4 — n-heptylcyclohexyl)phenoxy]benzene [化35] ❹

Η2ΝχχΗ2 -p-PDA

PCH7DAB (organic solvent) NMP : N -methyl-2-pyrrolidone BCS : butyl cellulolytic &lt; molecular weight measurement of polyimine] The molecular weight of the polyimine in the synthesis example is made by Showa Denko Co., Ltd. - 71 - 200948859 A room temperature gel permeation chromatography (GPC) device (GPC _ 1〇1), a column made by Shodex (KD-803, KD-805), was measured as follows.

Column temperature: 50 ° C Dissolved solution. N, N'- methyl methamine (as an additive, lithium bromide-hydrate (LiBr · HW) is 30 mmol / liter, phosphoric acid • anhydrous crystals (〇_phosphoric acid) ) 30 mmol / liter, tetrahydrofuran (THF) 1 〇 ml / liter) Flow rate: 1.0 ml / min Calibration line production standard sample: TSK manufactured by Tosoh Corporation, standard poly epoxy plant (molecular weight 900,000, 150,000, 100,000, 30, 〇〇〇) and polyethylene glycol manufactured by Polymer Laboratories, Inc. (molecular weight: about 12,000 &gt; 4,000 &gt; 1,000 ) ° &lt;Measurement of oxime imidization rate &gt; The imidization ratio of quinone imine is determined as follows. 20 mg of the polyimine powder was added to the NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd., φ 5 ), and 0.53 ml of dimethylated dimethyl hydrazine was added (〇1^150—(16, 0.05) %丁1^8 mixture), and completely dissolved by ultrasonic waves. The proton NMR of the solution was measured using a NMR measuring instrument (JNW-ECA500) manufactured by JEOL DATUM Co., Ltd. The source of yttrium imidization was used. Estimation of the peak of the proton determined by the protons of the unaltered structure before and after imidization as the reference proton and the estimation of the proton peak of the NH group derived from proline from 9.5 to 10 ppm. It is obtained by the following formula.

醯imination rate (%) = (1-α · x/y)xlOO In the above formula, x is the proton peak estimate derived from the NH group of the proline, y is the reference proton peak estimate α, α is the poly The ratio of the number of protons of one proton relative to the sulfhydryl group of valine (when the imineization rate is 0%) &lt;Synthesis Example 14&gt; BODA ( 3.83g &gt; 15.3 mmol ) , DBA ( 1.0 9 g, 7 1 7 mmol), PCH7DAB ( 3.88 g, 10.2 mmol), and the diamine compound (4) (0.74 g, 3.06 mmol) were mixed in NMP (17.5 g), and reacted at 8 ° C for 5 hours. Thereafter, CBDA (1.00 g, 5.10 mmol) was added and NMP (14.Og)' was reacted at 40 ° C for 6 hours to prepare a polyaminic acid solution. NMP was added to the polyamic acid solution (10.0 g), and after diluting to 6% by mass, acetic anhydride (1.67 g) as a ruthenium amide catalyst and pyridine (〇.90 g) were added thereto to make 90 The reaction was carried out in methanol (130 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 (A). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 18,500, and a weight average molecular weight of 48,200. -73-200948859 &lt;Synthesis Example 1 5&gt; In the polyphthalic acid solution (i〇.0g) obtained in Synthesis Example 14, after adding nmP to 6 mass%, acetic anhydride (2 17 g) was added to the ruthenium catalyst. And pyridine (1.68 g) was allowed to react at 9 (TC for 3.5 hours. The reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol, The polyiminoimine powder (B) was dried under reduced pressure at TC. The polyamidimide had an oxime imidization ratio of 80%, a number average molecular weight of 17,100, and a weight average molecular weight of 46,900. &lt;Synthesis Example 1 6 &gt; BODA (2.41g, 9.64 mmol), DBA (1.37 g, 9.0 1 mmol) 'PBCH7DAB (0.48g » 1.27 mmol), and diamine compound (7) (〇.66g, 2.72 mmol) The mixture was mixed with NMP (9.00 g), and after reacting at 80 ° C for 5 hours, CBDA (0.63 g, 3.21 mmol) and NMP (7.80 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polydecylamine. An acid solution was added to the obtained polyaminic acid solution (10.0 g), and after diluting to 6 mass%, acetic anhydride (1·60 g) and pyridine (〇.90 g) of a quinone imine catalyst were added thereto to make it The reaction was carried out for 3.5 hours at 90 ° C. The reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 10 ° C to obtain a polyimine powder. (C) The polyimine has a ruthenium iodide ratio of 56%, a number average molecular weight of 17,300, and a weight average molecular weight of 46,000. -74- 200948859 &lt;Synthesis Example 17&gt; BODA (4.59 g, 18.4 mmol) , DBA (1 · 30 g, 8.5 5 mmol), PCH7DAB ( 4.66 g, 1 2_2 mmol), and diamine compound (10) (0.94 g, 3.88 mmol) were mixed in NMP (21.5 g) at 8 〇 After reacting for 5 hours at ° C, CBDA (1.20 g, 6.12 mmol) and NMP (17.Og) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a poly-proline solution. NMP was added to the solution (10.0 g), and after diluting to 6 mass%, acetic anhydride (1.68 g) and pyridine (92 g) of a ruthenium catalyst were added, and the mixture was reacted at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (130 ml), and the resulting precipitate was removed. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyamidimide had a hydrazine imidation ratio of 60%, a number average molecular weight of 18,100, and a weight average molecular weight of 47,800. &lt;Synthesis Example 1 8 &gt; NMP was added to the polyamidic acid solution (10.0 g) obtained in Synthesis Example 17, and after diluting to 6 mass%, acetic anhydride (2.16 g) of ruthenium catalyst was added, and pyridine was added. (1.75 g), it was allowed to react at 90 t for 3.5 hours. The reaction solution was poured into methanol (130 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (E). The polyimine had an oxime imidization ratio of 83%, a number average molecular weight of 1,7,300, and a weight average molecular weight of 45,900. -75- 200948859 &lt;Synthesis Example 19&gt; BODA (2.56 g, 10.3 mmol), DB A (0.94 g, 6.1 8 mmol), PCH7DAB (1.56 g, 4.10 mmol), and diamine compound (14) (0.74 g) ,3·04 mmol) was mixed in NMP (10.50 g), and after reacting at 80 ° C for 5 hours, CBDA (0.67 g, 3.42 mmol) and NMP (9.00 g) were added, and the reaction was carried out at 40 ° C for 6 hours. And a polyaminic acid solution was prepared. NMP was added to the obtained polyaminic acid solution (l〇.〇g), and after diluting to 6 mass%, acetic anhydride (1·16 6 g) of ruthenium amide and pyridine (〇.88 g) were added thereto. It was reacted at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (140 ml), and the obtained 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 hydrazine imidation ratio of 55 %, a number average molecular weight of 19,100, and a weight average molecular weight of 49,100. &lt;Synthesis Example 20&gt; BODA (2.49 g, 9.94 mmol), DBA (1.llg, 7.30 mmol) 'PCH7DAB (0.75 g &gt; 1.97 mmol), and diamine compound (16) (0.85 g, 3.52 mmol) After mixing in NMP (9.50 g) and reacting at 80 ° C for 5 hours, CBDA (0.65 g, 3.31 mmol) and NMP ( 8.10 g) were added and reacted at 40 ° C for 6 hours to obtain polyfluorene. Amino acid solution. NMP was added to the obtained polyaminic acid solution (10.0 g), diluted to 6% by mass, and then acetic anhydride (1.12 g) of ruthenium amide was added, and pyridine (-76-200948859 0.9 0g), 80 The reaction was carried out at ° C for 2 hours. The reaction solution was poured into methanol (1 20 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 (G). The polyimine had a ruthenium iodide ratio of 53%, a number average molecular weight of 18,800, and a weight average molecular weight of 47,900. &lt;Synthesis Example 21&gt; BODA (2.53 g, 10.1 mmol), DBA (0.72 g, 4.74 mmol) 'PCH7DAB ( 2.56 g 1 6.73 mmol), and a diamine compound (19) (0.43 g, 1.79 mmol) After mixing in NMP (12.1 g) and reacting at 8 ° C for 5 hours, CBDA (0.66 g, 3.37 mmol) and NMP ( 9.20 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a poly Proline solution. Adding NMP to the obtained polyaminic acid solution (10.Og), diluting to 6 mass%, adding acetic anhydride (1.16 g) of ruthenium catalyst, and pyridine (1.0 g) The reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (140 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (H). The polyamidimide had a ruthenium iodide ratio of 55%, a number average molecular weight of 16,900, and a weight average molecular weight of 46,500. &lt;Synthesis Example 22&gt; BODA (2_60 g, 10.4 mmol), DBA (0.74 g, 4.87 mmol) 'PCH7DAB ( 2.64 g » 6.93 mmol), and diamine compound -77-200948859 (23) (0.47 g, 1.96 mmol) The mixture was mixed in NMP (ll.lg), and reacted at 8 ° C for 5 hours, then CBDA (0.68 g, 3.47 mmol) and NMP (9.50 g) were added, and the reaction was carried out at 40 ° C for 6 hours. A polyamine solution was obtained. After adding NMP to the obtained polyaminic acid solution (10.g.), and diluting to 6 mass%, acetic anhydride (i.i 5g) and pyridine (l.〇lg) of the quinone imine catalyst were added to make it The reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (1 20 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol at a reduced pressure at 100 ° C to obtain a polyimide pigment (I). The polyamidimide had a ruthenium iodide ratio of 54%, a number average molecular weight of 18,100, and a weight average molecular weight of 48,100. &lt;Synthesis Example 23&gt; BODA (2.49 g, 9.94 mmol), DBA (1.llg, 7.30 mmol) 'PCH7DAB (0.50 g &gt; 1.31 mmol), and diamine compound (26) (1_06 g, 4.37 mmol) The mixture was mixed in NMP (9.50 g), and reacted at 80 ° C for 5 hours, and then CBDA (0-65 g, 3.31 mmol) and NMP ( 8.10 g) were added and reacted at 40 ° C for 6 hours to obtain a reaction. Polylysine solution. NMP was added to the obtained polyaminic acid solution (1 〇.2g), and after diluting to 6 mass%, acetic anhydride (1.17 g) of ruthenium catalyst and pyridine (〇.99g) were added to make it The reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (130 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (J). The polyamine 200948859 has an imidization ratio of 57%, a number average molecular weight of 18,100, and a weight average molecular weight of 47,000. &lt;Synthesis Example 24&gt; BODA (2.55 g, 9.79 mmol), DBA (1.59 g, 10.5 mmol), PCH7DAB (0.49 g, 1.29 mmol), and a diamine compound (29) (0.42 g, 1.74 mmol) After mixing in NMP (8.50 g) and reacting at 8 ° C for 5 hours, CBDA (0.64 g, 3.26 mmol) and NMP (7.50 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a poly Proline solution. NMP was added to the obtained polyaminic acid solution (l〇.〇g), and after diluting to 6 mass%, acetic anhydride (1·16g) and pyridine (1.0 g) of the quinone imine catalyst were added. It was reacted at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (130 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (K). The polyamidimide had a ruthenium iodide ratio of 55%, a number average molecular weight of 1,800, and a weight average molecular weight of 47,900. &lt;Synthesis Example 25&gt; BODA (2.49 g, 9.94 mmol), DBA (0.61 g &gt; 4.0 1 mmol), PCH7DAB (2.52 g, 6.63 mmol), and diamine compound (34) (0.85 g &gt; 3_52 mmol) After mixing in NMP (12.5 g) and reacting at 8 ° C for 5 hours, CBDA (0.65 g, 3.31 mmol) and NMP (10.5 g) were added and reacted at 40 ° C for 6 hours to obtain a reaction. Polyamide-79- 200948859 acid solution. To the obtained polyamic acid solution (10.0 g), NMP was added, and after diluting to 6 mass%, acetic anhydride (1.16 g) of ruthenium catalyst and pyridine (1.0 g) were added thereto at 90 ° C. The reaction was carried out for 3.5 hours. The reaction solution was poured into methanol (150 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (L). The polyamidimide had a hydrazine imidation ratio of 55 %, a number average molecular weight of 18,400, and a weight average molecular weight of 47,400. &lt;Synthesis Example 26&gt; B OD A (4.40 g, 1 7.6 mm ο 1 ), DBA (1.25 g, 8.22 mmol) 'PCH7DAB ( 4.46 g 5 11.7 mmol), and diamine compound (3 7 ) (1.08 g &gt; 4.46 mmol) was mixed in NMP (21.0 g), and reacted at 8 ° C for 5 hours, then CBDA ( 1.15 g, 5 - 86 mmol ) and NMP ( 16.5 g ) were added at 40 ° C for 6 hours. The reaction was carried out to prepare a polyaminic acid solution. Add NMP to the obtained polyaminic acid solution (l〇.〇g), dilute to 6 mass%, add acetic anhydride (1.5 g) of ruthenium catalyst, and pyridine ( 1.〇〇8) The reaction mixture was poured into methanol (150 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 1 ° C. Polyimine powder (M). The polyimine has a hydrazine imidation ratio of 55 %, a number average molecular weight of 19,800, and a weight average molecular weight of 48,800. -80 - 200948859 &lt;Synthesis Example 27&gt; NMP was added to the obtained polyamic acid solution, and after diluting to 6% by mass, acetic anhydride (2.17 g) of ruthenium amide and pyridine (1 - 66 g) were added, and it was reacted at 9 (TC for 3.5 hours). The reaction solution was poured into methanol (31 Oral), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 10 ° C to obtain a polyimine powder (N). The ruthenium imine has an imidization ratio of 82%, a number average molecular weight of 16,800, and a weight average molecular weight of 46,300. &lt;Synthesis Example 28&gt; BODA ( 2.45 g, 9 .79 mmol ), DBA (0.70 g, 4.61 mmol) 'PCH7DAB ( 2.48 g &gt; 6.53 mmol), and the diamine compound (40) (0.50 g &gt; 2.08 mmol) were mixed in NMP (11.5 g) at 80 After reacting for 5 hours at ° C, CBDA (0.64 g, 3.26 mmol) and NMP (8.50 g) were added and reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. NMP was added to (lO.lg), and after diluting to 6 mass%, acetic anhydride (2.15 g) of ruthenium catalyst and pyridine (1.77 g) were added, and it was made to react at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (0). The hydrazine imidation ratio was 80%, the number average molecular weight was 16,900, and the weight average molecular weight was 47,200. -81 - 200948859 &lt;Synthesis Example 29&gt; BODA (2.49 g, 9.94 mmol), p-PDA (0.50 g, 4.64 mmol) , PCH7DAB (2.52g, 6.63 mmol), and diamine compound (40) (0.51 g, 2.11 mmol) were mixed in NMP (11.3 g), and reacted at 80 ° C for 5 hours, then added CBDA ( 0.65 g, 3.31 mmol) and NMP (8.30 g) were reacted at 40 ° C for 6 hours to prepare a polyaminic acid solution. NMP was added to the obtained polyaminic acid solution (l〇.〇g), and after diluting to 6 mass%, acetic anhydride (2.16 g) of ruthenium catalyst and pyridine (1.67 g) were added to make it 90. The reaction was carried out at ° C for 3.5 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (P). The polyamidimide had a ruthenium imidation ratio of 79%, a number average molecular weight of 17,100, and a weight average molecular weight of 47,900. &lt;Synthesis Example 30&gt; BODA (2.53 g, 10.1 mmol), DBA (0 · 7 2 g, 4 · 7 4 mmol), PCH7DAB (2.56 g, 6.73 mmol), and diamine compound (43) (0.49 g) , 2.01 mmol), mixed with NMP (11.8 g), and reacted at 8 ° C for 5 hours, then added CBDA (0-66 g, 3.37 mmol) and NMP ( 8.60 g), and reacted at 40 ° C for 6 hours. A polyaminic acid solution was prepared. NMP was added to the obtained polyaminic acid solution (10.0 g), and after diluting to 6 mass%, acetic anhydride (2.15 g) of a quinone imine catalyst, and pyridine (-82-200948859 l-65 g) were added to make it. The reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 Torr to obtain a polyimine powder (Q). The polyamidimide had a ruthenium iodide ratio of 81%, a number average molecular weight of 17,900, and a weight average molecular weight of 48,100. &lt;Synthesis Example 31&gt; BODA (2.49 g, 9.94 mmol), p-PDA (0.50 g, 4.64 mmol), PCH7DAB (2.51 g, 6.63 mmol), and diamine compound (43) (0.48 g &gt; 1.98) Methyl) was mixed with NMP (10.5 g), and reacted at 80 ° C for 5 hours, then CBDA (0.65 g, 3.31 mmol) and NMP ( 8.10 g) were added and reacted at 40 ° C for 6 hours. A polyamine solution was obtained. NMP was added to the obtained polyamic acid solution (10.gg), and after diluting to 6 mass%, acetic anhydride (2.18g) of ruthenium catalyst, and pyridine (1.868g) were added to 90 degreeC. The reaction was carried out for 3.5 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at TC to give a polyimine powder (R). The polyamidimide had an imidization ratio of 80% and a number average molecular weight of 17,700. The molecular weight is 47,600. -83- 200948859 Table 5] Synthesis Example Diamine j 戎 (mmol) Tetracarboxylic acid component (mmol) 醯 imidization ratio (%) Diamine compound (A) Diamine compound (B) Other 14 Polyimine powder ΓΑ1 chemical fiber 4) (3.06) DBA (7.17) PCH7DAB (10.2) CBDA (5.10) BODA (15.3) 55 15 Polyimine powder ΓΒ1 Compound (4) (3.06) DBA (7.17) PCH7DAB (10.2 CBDA (5.10) BODA (15.3) 80 16 Polyimine powder rci Compound (7) (2.72) DBA (9.01) PCH7DAB (1.27) CBDA (3.21) BODA (9.64) 56 17 Polyimine powder "D1 compound (10) ( 3.88) DBA (8.55) PCH7DAB (12.2) CBDA (6.12) BODA (18.4) 60 18 Polyimine powder ΓΕ1 Compound (10) (3.88) DBA (8.55) PCH7DAB (12.2) CBDA (6.12) BODA (18.4) 83 19 Polyimine powder TF1 Compound (14) (3-04) DBA (6.18) PCH7DAB (4.10) CBDA (3.42) BODA (10.3) 55 20 Polyimine powder "G1 compound (16) (3.52) D BA (7.30) PCH7DAB a.97) CBDA (3.31) BODA (9.94) 53 21 Polyimine powder ΓΗ1 Compound (19) (1_79) DBA (4.74) PCH7DAB (6.73) CBDA (3.37) BODA (10.1) 55 22 Polyimine powder ΓΙ1 Compound (23) (1-96) DBA (4.87) PCH7DAB (6.93) CBDA (3.47) BODA (10-4) 54 23 Polyimine powder m Compound (26) (4.37) DBA ( 7.30) PCH7DAB (1.31) CBDA (3.31) BODA (9.94) 57 24 Polyimine powder ΓΚ1 Compound (29) (1.74) DBA (10.5) PCH7DAB (1.29) CBDA (3.26) BODA (9.79) 55 25 Poly Amine powder "L1 compound (34) (3.52) DBA (4.01) PCH7DAB (6.63) CBDA (3.31) BODA (9.94) 55 26 Polyimine powder "Ml compound (37) (4.46) DBA (8.22) PCH7DAB a 1.7 CBDA (5.86) BODA (17.6) 55 27 Polyimine powder [N1 compound (37) (4.46) DBA (8.22) PCH7DAB (11.7) CBDA (5.86) BODA (17.6) 82 -84- 200948859 [Table 6] Synthesis Example Diamine Component (mmol) Tetracarboxylic Acid Component (mmol) Ruthenium Amination Rate (%) 28 Polyimine Powder Γ〇1 Compound (40) (2.08) DBA (4.61) PCH7DAB (6.53) CBDA Ρ· 26) BODA (9.79) 80 29 Polyimine powder [P1 (4〇) (2.11) p-PDA (4.64) PCH7DAB (6.63) CBDA (3.31) BODA (9.94) 79 30 Polyimine Powder Γ01 Compound (43) (2.01) DBA (4.74) PCH7DAB (6.73) CBDA (3.37) BODA (10.1) 81 31 Polyimine powder is called compound (43) (1.98) p-PDA (4.64) PCH7DAB (6.63) CBDA (3.31) BODA (9.94) 80 [Production and evaluation of liquid crystal alignment agent &lt;Example 1&gt; NMP (22.1 g) was added to the polyimine powder [A] (5.5 g) obtained in Synthesis Example 14, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (ll.lg) and BCS (46.8 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [1]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. [Production of Liquid Crystal Cell] The liquid crystal alignment treatment agent [1] obtained above was spin-coated on the ITO surface of a substrate to which a 3 cm X4 cm (length X width) ITO electrode was attached, and 80° on a hot plate. After 5 minutes at C, the film was fired in a hot air circulating oven at 21 ° C for 1 hour to prepare a polyimide film having a film thickness of 10 nm. The substrate to which the liquid crystal alignment film was attached was rubbed in a friction device having a roll diameter of 120 mm and a crepe cloth at a speed of 30 mm/sec, a roll speed of 20 mm/sec, and -85-200948859. The substrate is attached to the liquid crystal alignment film. Two sheets of the substrate to which the liquid crystal alignment film was attached were prepared, and a 6 # m bead spacer was spread on one of the liquid crystal alignment film faces, and a sealant was printed thereon. The other substrate was subjected to internal measurement of the liquid crystal alignment film, and after the rubbing direction was reversed, the sealing agent was hardened to prepare an empty cell. A liquid crystal MLC-6608 (manufactured by Merck & Co., Ltd.) was injected into the empty cell by a vacuum injection method to prepare an antiparallel aligned nematic liquid crystal cell. [Evaluation of Voltage Holding Rate] A voltage of 4 V of 60 /zs was applied to the liquid crystal cell obtained above at a temperature of 80 ° C, and the voltages after 16.67 ms and 1 667 ms were measured, and the degree of voltage which can be maintained as a voltage was calculated. Maintenance rate. The results are shown in Table 7 below. [Evaluation of Retention of Residual Charge] A DC voltage of 10 V was applied to the liquid crystal cell after the voltage holding ratio was measured for 3 ’ minutes, and after a short circuit for 1 second, the potential generated in the liquid crystal cell was measured in 1 800 sec. The residual charge was measured after 50 seconds and after 1 000 seconds. Further, the measurement was carried out using a 62 5 4 liquid crystal physical property evaluation device manufactured by Dongyang Technology Co., Ltd. The results are shown in Table 8 below. [Evaluation after high-temperature placement] The liquid crystal cell after the measurement of the residual charge was placed in a high-temperature bath set at 100 °C for 7 days, and then the voltage maintenance ratio and the residual charge were measured. Results 200948859 is listed in Tables 7 and 8 below. &lt;Example 2&gt; NMP (21.7 g) was added to the polyimine powder [B] (5.0 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (10. 8g) and BCS (45.8 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [2]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [2], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. As a result, it is not shown in Table 7 and Table 8 which will be described later. <Example 3> NMP (2.94 g) was added to the polyimine powder [C] (4.9 g) obtained in Synthesis Example 16 at 70 ° C. Stir for 40 hours to dissolve. NMP (14.8 g) and BCS (32.5 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [3]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. As a result, as shown in Table 7 and Table 8 below, 0-87-200948859 &lt;Example 4&gt; NMP (21.6 g) was added to the polyimine powder [D] (5.〇g) obtained in Synthesis Example 17. It was stirred at 70 ° C for 40 hours to dissolve. NMP (10.5 g) &gt; BCS (45.4 g) was added to the solution and stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [4]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [4]', a liquid crystal cell was prepared in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. The results were as follows: &lt;Example 5&gt; In the polyimine powder [E] (5.0 g) obtained in Synthesis Example 18, NMP (2.72 g) was added at 70 ° C. Stir for 40 hours to dissolve. NMP (13.5 g) and BCS (37.6 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [5]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a dissolution state of the uniform sentence. Using the obtained liquid crystal alignment treatment agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of residual charge was alleviated, and the evaluation after high temperature standing was performed. The results are as shown in Tables 7 and 8 below. &lt;Example 6&gt; Into the polyimine powder [F] (5 · 1 g) obtained in Synthesis Example 19, -88-.200948859 NMP (25.Og) was added, and the mixture was stirred at 70 ° C for 40 hours. It dissolves. NMP (12.5 g) 'BCS (42.5 g) was added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [6]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [6], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. As a result, as shown in the following Tables 7 and 8 &lt;Examples, in the polyimine powder [G] (5.0 g) obtained in Synthesis Example 20, NMP (24.4 g) was added, and the mixture was stirred at 70 ° C for 40 hours. Let it dissolve. NMP (12.2 g) and BCS (41.8 g) were added to the solution, and the mixture was stirred at 25 t for 2 hours to obtain a liquid crystal alignment treatment agent [7]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [7], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. The results are shown in Tables 7 and 8 below. &lt;Example 8&gt; NMP (30.1 g) was added to the polyacrylonitrile powder [H] (5.0 g) obtained in Synthesis Example 21, and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (14_7g) and BCS (33.5g) were added to the solution, and the mixture was stirred at 25 ° C for 2 -89 - 200948859 hours to obtain a liquid crystal alignment treatment agent [8]. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [8], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of the residual charge was alleviated, and the evaluation after high temperature standing was performed. As a result, it will not be as shown in Table 7 and Table 8 below.

&lt;Example 9&gt; In the polyimine powder [I] (5.0 g) obtained in Synthesis Example 22, NMP (32.7 g) was added, and the mixture was stirred at 7 (TC) for 40 hours to dissolve. NMP (16_5g), BCS (29.2g), stirred at 25 °C 2

After a few hours, a liquid crystal alignment treatment agent [9] was obtained. The liquid crystal alignment agent did not exhibit abnormalities such as turbidity or precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treating agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage holding ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. The results are shown in Tables 7 and 8 below. &lt;Example 1 〇&gt; In the polyimine powder [J] (4.8 g) obtained in Synthesis Example 23, NMP (3 1.5 g) was added and stirred at 70 ° C for 40 hours to dissolve. NMP (15.5 g) and BCS (28.1 g) were added to the solution, and the mixture was passed through 25. (After stirring for 2 hours, a liquid crystal alignment treatment agent [10] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component exhibited a uniform dissolution state - 90-200948859. The alignment treatment agent [10] was prepared in the same manner as in Example 1 to evaluate the voltage retention rate, to evaluate the residual charge, and to evaluate after the high temperature deposition. The results are shown in Tables 7 and 8 below. &lt;Example 11&gt; In the polyimine powder [κ] (5.0 g) obtained in Synthesis Example 24, NMP (38.3 g) was added, and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (19.2 g) and BCS (20.7 g) were added to the solution at 25 (after stirring for 2 hours) to obtain a liquid crystal alignment treatment agent [1 1 ]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent. It was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [1 1 ], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the residual charge was evaluated, and the high temperature was placed. Post evaluation. The result, Table 7 and Table 8 which will be described later. ❹ &lt;Example 12&gt; In the polyimine powder [L] (4.9 g) obtained in Synthesis Example 25, NMP (32_2 g) was added and stirred at 70 ° C for 40 hours. To the solution, NMP (16.1 g) and BCS (28.5 g) were added, and after stirring for 2 hours at 25 t, the liquid crystal alignment treatment agent [1 2 ] was obtained. No turbidity was observed in the liquid crystal alignment treatment agent. Or an abnormality such as precipitation, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [1 2 ], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated to relax the residual electricity. 91 - 200948859 Evaluation of the charge and evaluation after high temperature deposition. The results are shown in Tables 7 and 8 below. &lt;Example 13&gt; Polyimine powder obtained in Synthesis Example 26 [M] (5.0 g) NMP (30.0 g) was added and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (14.8 g) and BCS (33.3 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours. Liquid crystal alignment treatment agent [13]. The liquid crystal alignment treatment agent did not detect abnormalities such as turbidity or precipitation, and confirmed that the resin composition was present. The liquid crystal cell was prepared in the same manner as in Example 1 using the obtained liquid crystal alignment treatment agent [13], and the voltage retention rate was evaluated, the residual charge was evaluated, and the evaluation was performed after the high temperature was placed. As shown in the following Tables 7 and 8. [Example 14] In the polyimine powder [N] (5.0 g) obtained in Synthesis Example 27, NMP (32.6 g) was added, and the mixture was stirred at 70 ° C. It was dissolved in 40 hours. NMP (16.6 g) and BCS (29.2 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [1 4]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component exhibited a uniform dissolution state. Using the obtained liquid crystal alignment treatment agent [1 4], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage holding ratio was evaluated, the residual charge was evaluated, and the evaluation after high temperature standing was performed. The results are shown in Tables 7 and 8 below. -92-200948859 <Comparative Example 1 &gt; In the polyimine powder [〇] (4.5 g) obtained in Synthesis Example 28, NMP (24.5 g) was added, and the mixture was stirred at 7 (TC) for 40 hours to dissolve. NMP (12.3g) and BCS (33.8g) were added to the solution, and the liquid crystal alignment treatment agent [15] was obtained after stirring for 2 hours. The liquid crystal alignment treatment agent was not found to be turbid or precipitated. Abnormally, it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [1 5 ], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention rate was evaluated, the residual charge was evaluated, and the temperature was elevated. The evaluation was carried out, and the results are shown in Tables 7 and 8 below. &lt;Comparative Example 2 &gt; In the polyimine powder [P] (4.6 g) obtained in Synthesis Example 29, NMP (35.3 g) was added. The solution was dissolved by stirring at 70 ° C for 40 hours. NMP (17.6 g) and BCS (19.3 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [1 6 No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component exhibited a uniform dissolved state. Using the obtained liquid crystal alignment treatment agent [6 6], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated, the evaluation of the residual charge was relaxed, and the evaluation after the high temperature was placed. The result is as follows. 7 and Table 8. <Comparative Example 3 &gt; -93- 200948859 In the polyimine powder [Q] (4.5 g) obtained in Synthesis Example 30, NMP (27 g) was added at 70 ° C After stirring for 40 hours, NMP (13.3 g) and BCS (30.1 g) were added to the solution, and after stirring at 25 ° C for 2 hours, a liquid crystal alignment treatment agent [17] was obtained. The liquid crystal alignment treatment agent No abnormality such as turbidity or precipitation was observed, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [17], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage retention ratio was evaluated. The evaluation of the residual charge was evaluated, and the evaluation was carried out after the high-temperature standing. As a result, Table 7 and Table 8 described later &lt;Comparative Example 4&gt; In the polyimine powder [R] (4.5 g) obtained in Synthesis Example 31, NMP was added. (37.lg), dissolved at 70 ° C for 40 hours to dissolve. Add this solution NMP (18_5g) and BCS (35.0g) were obtained at 25. After stirring for 2 hours, a liquid crystal alignment treatment agent [18] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the resin composition was confirmed. A uniform dissolved state was exhibited. Using the obtained liquid crystal alignment treatment agent [8 8], a liquid crystal cell was produced in the same manner as in Example 1, and the voltage holding ratio was evaluated, the evaluation of residual charge was relaxed, and the evaluation after high temperature standing was performed. The results are shown in Tables 7 and 8 below. -94- 200948859 Table 7]

Liquid crystal alignment treatment agent voltage retention ratio (%) 16.67 ms 1667 ms 16.67 ms 1667 ms after liquid crystal cell fabrication at a high temperature. Example 1 [1] 97.8 64.5 97.7 64.2 Example 2 [2] 98.2 66.7 98.1 66.5 Example 3 [3] 97.7 64.6 97.5 64.7 Example 4 [4] 97.9 64.4 97.9 64.3 Example 5 [5] 98.3 66.9 98.3 66.8 Example 6 [6] 97.5 64.3 97.4 64.2 Example 7 [7] 97.2 64.1 97.0 63.9 Example 8 [8] 97.3 64.1 97.2 64.0 Example 9 [9] 97.6 64.5 97.5 64.3 Example 10 [10] 97.9 64.9 97.8 64.8 Example 11 [11] 97.3 64.5 97.6 64.2 Example 12 [12] 97.3 64.3 97.3 64.1 Example 13 [13] 97.4 64.4 97.5 64.4 Example 14 『141 98.3 66.7 98.2 66.5 Comparative Example 1 [15] 97.6 66.1 97.1 64.8 Comparative Example 2 [16] 97.2 66.2 96.4 64.0 Comparative Example 3 [17] 97.1 65.4 96.1 63.8 Comparative Example 4 Γ181 96.9 65.1 96.2 63.2

-95- 200948859 Table 8] Liquid crystal alignment agent to alleviate residual 1 1 charge (V) After liquid crystal cell fabrication, after 50 seconds, 1000 seconds, 50 seconds, and 1000 seconds later, Example 1 [1] 1.78 0.21 1.82 0.23 Example 2 [2] 3.85 0.72 3.83 0.73 Example 3 [3] 1.12 0.15 1.14 0.16 Example 4 [4] 2.01 0.31 2.12 0.31 Example 5 [5] 3.94 0.88 3.99 0.92 Example 6 [6] 1.45 0.18 1.48 0.21 Example 7 [7] 1.24 0.14 1.22 0.14 Example 8 [8] 1.84 0.24 1.90 0.32 Example 9 [9] 1.88 0.23 1.85 0.26 Example 10 [1〇] 1.19 0.12 1.21 0.15 Example 11 [Π] 1.15 0.11 1.17 0.12 Example 12 [12] 1.84 0.29 1.88 0.33 Example 13 [13] 2.12 0.40 2.20 0.42 Example 14 『141 3.94 0.76 3.99 0.78 Comparative Example 1 [15] 3.98 1.56 4.13 1.89 Comparative Example 2 [16] 4.15 1.85 4.29 2.01 Comparative Example 3 [17] 4.03 1.78 4.22 1.99 Comparative Example 4 "181 4.28 1.93 4.39 2.12 [Industrial Applicability] When the liquid crystal alignment treatment agent of the present invention is used as a liquid crystal alignment film, a voltage holding ratio can be obtained even if After prolonged exposure to high temperatures, it can also accelerate the mitigation by straight A liquid crystal alignment film which accumulates residual charge due to a flow voltage. It is also provided with a highly reliable liquid crystal display element which can withstand long-term use in an excessively harsh environment. As a result, it can be used for a TN element, an STN element, and a TFT liquid crystal element. Further, it can be used for a vertical alignment type or a horizontal alignment type (IPS) liquid crystal display element, etc. -96- 200948859 Also, the specification and patent application scope of the Japanese Patent Application No. 2008-0181, filed on January 25, 2008, The entire contents of the Abstract are incorporated herein by reference.

-97-

Claims (1)

200948859 VII. Patent application scope: 1. A liquid crystal alignment treatment agent characterized by 'copolymerization containing a diamine component containing a diamine compound (A) and a diamine compound (B) and reacting with a tetracarboxylic dianhydride component The diamine compound (A): a diamine compound represented by the following formula: (II): a diamine compound having a carboxyl group in the molecule, [Chemical Formula 1] (In the formula [1], at least one divalent organic group selected from the group consisting of _0-, an NQ1-, a CONQ1-, an NC^CO-, _CH2〇_, and -〇CO-, Qi is a hydrogen atom Or an alkyl group having 1 to 3 carbon atoms, X2 being a single bond or at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups and aromatic hydrocarbon groups, X3 being a single bond or at least one selected from the group consisting of -〇-, -NQ2-, -C0NQ2-, _NQ2CO_ '-C00-, -0C0-, and -〇(CH2)m- (m is an integer from 1 to 5) The divalent organic group, Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X4 is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4. 2. The liquid crystal alignment treatment agent according to claim 1, wherein the formula [1] is at least selected from the group consisting of the compounds represented by the following formulas [la] to [lf]: 200948859 NH, [1 [lb] h2n Η2Ν0ΓΓΧ2_Χ3_Χ4) n NH, H2! [Id] H2-0-X2-X3-X4)n[1 e] [1 —X2-X3-X4) n [If] (wherein Q1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms' Xz is a single bond or an aliphatic hydrocarbon group selected from a carbon number of 1 to 20, a non-aromatic ring At least one divalent organic group 'X3 of a group of a hydrocarbon group and an aromatic hydrocarbon group is a single bond or is selected from the group consisting of -0-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, one OCO- and -0 (CH2)m- (m is an integer from 1 to 5) of at least one divalent organic group, Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X4 is a nitrogen-containing aromatic heterocyclic ring, η Is an integer from 1 to 4.) 3. The liquid crystal alignment treatment agent according to claim 2, wherein the oxime 2 in the formula [la] to the formula [If] is a single bond, a linear alkyl group having 1 to 3 carbon atoms or a benzene ring. 4. The liquid crystal alignment treatment agent of claim 2 or 3, wherein Χ3 in the formula [la] to the formula [If] is a single bond, -〇c〇- or -〇CH2-. The liquid crystal alignment treatment agent according to any one of claims 2 to 4, wherein χ4 in the formula [la] to the formula [If] is an imidazole ring, a pyridine ring or a pyrimidine ring. 6. The liquid crystal alignment treatment agent according to any one of the items 2 to 5 of the patent application, wherein n in the formula [la] to the formula [If] is an integer of 1 or 2. -99- 200948859 7. The liquid crystal alignment treatment agent of claim 2, wherein X2 in the formula [la] to the formula [If] is a linear or branched alkyl group selected from a carbon number of 1 to 1 Å, At least one of a group consisting of a cyclohexane ring, a benzene ring and a naphthalene ring, X3 being selected from the group consisting of a single bond, a fluorene-, a CONH-, a _NHCO-, a C Ο Ο —, —OCO—and a 0 (CH 2 ) M—(m is an integer from 1 to 5) in groups of at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a sorghum ring, a three-till ring, and a triazole ring. And at least one of a group consisting of a piperidine ring, a benzimidazole ring and a benzimidazole ring, and η is an integer of 1 or 2. 8. The liquid crystal alignment treatment agent according to claim 2, wherein the oxime 2 in the formula [la] to the formula [If] is a linear or branched alkyl group selected from a single bond, a carbon number of 1 to 5, and a benzene ring. At least one of the groups, Χ3 is selected from the group consisting of a single bond, -0-, a CONH-, an NHCO-, -COO-, an OCO_ and -0(CH2)m- (m is an integer from 1 to 5) At least one of the groups, X4 is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. 9. The liquid crystal alignment treatment agent of claim 2, wherein the oxime 2 in the formula [la] to the formula [If] is selected from the group consisting of a single bond, a linear alkyl group having 1 to 3 carbon atoms, and a benzene ring. At least one of the group, Χ3 is at least one selected from the group consisting of a single bond, -OCO-, and -OCH2, and χ4 is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and η is 1 or An integer of 2. 10. The liquid crystal alignment treatment agent according to any one of claims 1 to 9 wherein the diamine compound having a carboxyl group in the molecule is a diamine represented by the following formula [2], -100- [ 2] 200948859 (In the formula [2], X5 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and E is an integer of 1 to 4). 11. The liquid crystal alignment treatment agent according to claim 10, wherein the diamine compound of the formula [2] is at least one diamine compound selected from the group consisting of the following formula P] to the formula [7]. 6] (CHzWCOOH nh2 h2n COOH Η2Νΐ^|Ό (CH2)m5C' [5] (CH2)m6C〇〇H &quot;〇~cO~nH2 X7 [6] H2N0&quot;X80^X80NH2 (COOHW [7] (Formula [3] In the formula [4], X6 is a single bond, -101 - 200948859 - C Η 2 -, _ C 2 H 4 -, - C (CH3) 2 -, - CF2 - ' C ( CF 3) 2 I, O O —, CO — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — —, a CON(CH3)—, or an N(CH3)CO—, m2 and m3 are integers from 0 to 4, respectively, and m2+m3 represents an integer from 1 to 4, and in the formula [5], m4 and m5 are respectively An integer of 1 to 5, in the formula [6], X7 is a linear or branched alkyl group having 1 to 5 carbon atoms, m6 is an integer of 1 to 5, and in the formula [7], X8 is a single bond, -CH2 —, _ C 2 Η 4 —, a C ( C Η 3 ) 2 _, a CF 2 I, a C (CF 3 ) 2 —, 〇—, a CO—, a ΝΗ—, a N(CH3)— , a CONH-, NHCO-, a CΗ2〇—, a CΟ2, a COO—, an OCO—, —CON(CH3)—, or—N(CH3)CO—, m7 is an integer from 1 to 4. 1 2. If applying The liquid crystal alignment treatment agent of the above-mentioned item, wherein, in the formula [3], the ml is an integer of 1 to 2. 1 3 . The liquid crystal alignment treatment agent of the claim 1 of the patent application, wherein the formula [4] ] 'X6 is a single bond, a CH2-, - C2H4-, C(CH3)2-, a Ο-'-CO-, an NH-, a N(CΗ3)-, a CONH-, -NHCO-, A COO-, or -OCO-, m2 and m3 are integers of 1 at the same time. 1 4. A liquid crystal alignment treatment agent according to claim 1 of the patent scope, wherein, in the formula [7], X8 is a single bond, a CH2_ , -0_, -CO-, -NH-, -CONH-, one NHCO-, one C Η 2 Ο -, one 〇C Η 2 - , one COO-, or - OCO-, m7 is an integer from 1 to 2 The liquid crystal alignment treatment agent according to any one of claims 1 to 14, wherein the diamine component is in the range of from 1 to 102 to 200948859 mol of the diamine represented by the formula [1]. The diamine having a carboxyl group therein is from 0.01 to 99 moles. The liquid crystal alignment treatment agent according to any one of claims 1 to 15, wherein 5 to 8 〇% by mass of the solvent contained in the liquid crystal alignment treatment agent is a weak solvent. The liquid crystal alignment treatment agent according to any one of claims 1 to 16, wherein the copolymer in the liquid crystal alignment treatment agent is a polyimine obtained by dehydration ring closure of polyamic acid. A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 17. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 18 of the patent specification. ❹ -103- .200948859 IV. Designated representative 圊: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: None 200948859 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Formula 1] [Chemical 1] nh2 [1] H2N- X2-X3-X4 ) n