TW201033249A - Diamine, polyimide, liquid crystal aligning agent, and liquid crystal alignment film - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent which can provide, without addition of a crosslinking agent, a liquid crystal alignment film that has excellent mechanical strength and is not easily scratched by rubbing. The liquid crystal aligning agent can also provide a highly reliable liquid crystal alignment film that provides a liquid crystal display element having a low ion density and a high voltage holding ratio even at high temperatures. Also disclosed is a polymer or the like for obtaining the liquid crystal aligning agent. The liquid crystal aligning agent is characterized by containing a polyimide precursor which contains a sub stituent having a structure represented by formula (1), or an imidized polymer of the polyimide precursor. (In the formula, A represents a single bond or a divalent organic group; and R1, R2 and R3 each independently represents a hydrogen atom or a divalent organic group having 1-10 carbon atoms.)

Description

201033249 6. Technical Field of the Invention: The present invention relates to a liquid crystal alignment agent for producing a liquid crystal alignment film, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a polymer and a single polymer for manufacturing the liquid crystal alignment agent body. More specifically, it is a liquid crystal alignment film which is excellent in mechanical strength which is excellent in mechanical strength and which is less likely to cause frictional scratches, and which has a high voltage holding ratio and a low ion density at a high temperature and has excellent reliability. A liquid crystal alignment agent, and a polymer and a monomer for producing the liquid crystal alignment agent. [Prior Art] A liquid crystal display element used in a liquid crystal television, a liquid crystal display or the like is generally provided with a liquid crystal alignment film for controlling a liquid crystal alignment state. The liquid crystal alignment film imparts alignment to the liquid crystal by performing various alignment treatments on the surface of the film. At present, the most popular method for producing a liquid crystal alignment film in the industry is to wipe the surface of a resin film formed on an electrode substrate by using a cloth such as cotton, nylon or polyester, that is, a rubbing treatment, a widely used resin film, and self-polymerization. A polyimine film obtained by coating and firing a polyimine precursor such as proline or a polyimine solution. The method of rubbing the polyimide film is an industrially applicable method which is simple and highly productive. However, when the adhesion and mechanical strength of the polyimide film formed on the electrode substrate are insufficient, the film peeling and the scratch due to friction are caused by the rubbing treatment. A method for suppressing such film peeling and scratching from friction, and a method of adding a liquid crystal alignment agent containing an epoxy compound using polyamic acid or polyimine (refer to Patent Document η, A method of adding a liquid crystal alignment agent containing an epoxy compound of a nitrogen atom to a solution of polyacrylic acid or polyimine (see Patent Documents 2 and 3), and adding a solution of polyglycine or polyimine A method of a liquid crystal alignment agent containing a compound having a reactive group other than an epoxy group and an epoxy group (refer to Patent Document 4). Reactivity by adding such a polyimine precursor or a polyimine containing an epoxy group The crosslinking agent can enhance the mechanical strength of the polyimide film. The reason is that a polar group such as a carboxylic acid such as a polyimide or a polyimide may react with an epoxy group. [Patent Document 1] Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei 9-146 No. Document 4: Japanese Patent Publication No. 2007-11221_ Contents [Problems to be Solved by the Invention] Generally, a compound used as a crosslinking agent is a low molecular compound. Therefore, it is sublimed during baking, so that sufficient effect cannot be obtained when it is not excessively added. However, an unreacted crosslinking agent is excessively added. Since it is left in the film, the voltage holding ratio and the ion density are deteriorated as a liquid crystal display element, and good display properties may not be obtained. -6- 201033249 In view of such matters, it is an object of the present invention to provide When the crosslinking agent is not added, a liquid crystal alignment film having excellent mechanical strength which is less likely to be attached to the rubbing flaw during the rubbing treatment can be obtained, and the liquid crystal display element maintains a high voltage holding ratio and a low ion density at a high temperature and has high reliability. A liquid crystal alignment agent for a liquid crystal alignment film, and a polymer and a monomer for producing the liquid crystal alignment agent. [Method for Solving the Problem] The inventors of the present invention have found that the use has the advantage of being detachable by heating. Polydiimide compound and/or tetracarboxylic acid derivative of t-butoxycarbonyl (hereinafter also referred to as Boc group) The above object can be attained by a liquid crystal alignment agent of a primer or a polyimine. More specifically, a highly reactive aliphatic amine is formed by heating off the Boc group, and the aliphatic amine is used as a crosslinking point. When the friction is applied, the liquid crystal alignment film having excellent mechanical properties such as film peeling and scratches does not occur, and the liquid crystal display element using the liquid crystal matching φ film still maintains a high voltage holding ratio and a low ion density at a high temperature. In the meantime, the gist of the present invention is as follows: 1. A liquid crystal alignment agent characterized by containing a polyimine precursor having a substituent represented by the following formula (1) or the polyfluorene Iridium imidized polymer of imine precursor, [Chemical 1]

Ch3 - CH3(1) ch3 r2 -7- 201033249 (wherein A is a single bond or a divalent organic group, and R3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). (2) The liquid crystal alignment agent according to the above 1, wherein the polyimine precursor or the ruthenium imidized polymer of the polyimide precursor is a diamine having a substituent represented by the formula (1) At least one selected from the group consisting of a compound and a tetracarboxylic acid derivative having a substituent represented by the formula (1). The liquid crystal alignment agent according to the above 2, wherein the polyamidene precursor or the ruthenium imidized polymer of the polyimide precursor is used from the entire diamine compound and the tetracarboxylic acid derivative. 2 to 1 mol% of a diamine compound having a substituent represented by the formula (1) and/or a tetracarboxylic acid derivative having a substituent represented by the formula (1). 4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the polyimine precursor is a structure containing a structural unit of the following formula (2), 0 0

(wherein X! is an organic group of (4 + a) valence, Y is a (2+b) valence having a 201033249 machine group, R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and z is the above formula (1) The structure represented, a and b are each an integer from 〇 to 4, a + b > 0). 5. The liquid crystal alignment agent according to any one of items 1 to 3, wherein the polyimine precursor is a structure containing a structural unit of the following formula (3)

[Chemical 3]

(wherein X is a tetravalent organic group, γ2 is an organic group of (2 + c) valence, fU is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ζ is a structure represented by the above formula, and c is The liquid crystal alignment agent of any one of the items 1 to 3, wherein the polyimine precursor is a structure containing a structural unit represented by the following formula (4), [Chemical 4] ( 2) c coor4 --CO—X—CO— ! coor4

Rs-NH-- (4) (wherein, χ is a tetravalent organic group, 1 is a hydrogen atom or a carbon number 丨 to a bucket of -9-201033249 alkyl, R5 is a single bond or a carbon number of 1 to 20 The valence organic group 'Z is a structure represented by the above formula (1), and c is an integer of 1 to 4). 7. The liquid crystal alignment agent according to any one of items 1 to 3, wherein the polyimine precursor is a structure containing a structural unit represented by the following formula (5), [Chem. 5] (Z) COOR4 - CO-X—CO-NH—/ Λ • ^—y^NH- COOR4 (5)

(wherein X is a tetravalent organic group, 114 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a structure represented by the above formula (1), and C is an integer of 1 to 4). A liquid crystal alignment film obtained by baking the liquid crystal alignment agent according to any one of the above 1 to 7 at 150 to 300 ° C. A polyimine precursor comprising a structural unit represented by the following formula (6), [Chem. 6]

(6)

(wherein, X is a tetravalent organic group, Y2 is a (2 + c) valence organic group 'Z -10- 201033249 is a structure represented by the following formula (1), and R4 is a hydrogen atom or a carbon number of 1 to 4 alkyl, C is an integer from 1 to 4) [Chemical 7] ttL0 r2 ch3 -CH3 (1) ch3 (wherein A is a single bond or a divalent organic group, and R3 is each independently a hydrogen atom or carbon The number 1 to 20 of the monovalent organic group). 10. A polyimine which comprises a structural unit represented by the following formula (7), [Chem. 8]

(wherein X is a tetravalent organic group, Y2舄(2 + c) is an organic group, Z is a structure represented by the following formula (1), and <; is an integer of 丨4) ] —A~C—N 1 r2 I1 I3 〇CH3 H—ο--CH3 (1) ch3 (wherein 'A is a single bond or a divalent organic group, and each of ~, ^ and r3 is independently a hydrogen atom or a carbon number of 1 To 20% of the organic base). -11 - 201033249 11. A polyimine precursor comprising a structural unit represented by the following formula (8), [10] (Z)c coor4 • CO-X-CO-NH COOR4 (8 Ο _^r5-nh- (wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), and R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R5 is a divalent organic group having 1 to 20 carbon atoms, and c is an integer of 1 to 4) [A11] -A- -ο- Ι r2 tl -ο ch3 ——CH3(1) ch3 (wherein A is a single bond or The divalent organic group; ^, 112 and R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). A polyimine which contains a structural unit represented by the following formula (9), [Chemical 12]

'〇 〇 - one N

(Z)c

(9) 201033249 (wherein X is a tetravalent organic group, and R5 is a carbon number of 1 to 20 ί Z is an organic group represented by the following formula (1), and C is an integer of 1 to 4 I1 I3 —A—C—Ν- I R2

ΟII ch3 -ο- ch3 (1 ch3

(wherein, A is a single bond or a divalent valence is a hydrogen atom or a carbon number of 1 to 20; a structural unit represented by a polyimine precursor i, ί, R, R2, and R3 Each has a unique price of organic base). [, it is, contains the following formula (10) [Chem. 14]

(z)c coor4

I

——CO—X—CO—NH

I co〇R4 (wherein X is a tetravalent organic group, and R4 is a hydrogen atom or a carbon number of 1 to 10). Z is an alkyl group represented by the following formula (1), and C is 1 An integer of 4 to [11] 11 I3

Ch3 ch3 ch3 -13- 201033249 (wherein A is a single bond or a divalent organic group, and 1, 112 and R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). A polyimine which contains a structural unit represented by the following formula (11),

(wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), and c is an integer of 1 to 4). [Formation] R-) R3 Ο II II -A-C-Ν --0—Ο r2 ch3 ——CH3(1) ch3

(wherein a is a single bond or a divalent organic group; and 1, 2 and R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). A diamine compound which is represented by the following formulas (A) to (F), 201033249 [Chem. 18]

H2Nh^-NH2 (D) HzN-^-NHz

H2N (A) 13⁄4 Spear/=&lt; (ch2)3-Sjh h2n-^&gt;nh2 (B) h2n-〇-nh2 (C) H3^ μ p P^3 H3^CH3 (CH2)3HvJH (/〇 HsC±CH3 hn&quot;0 〇"H Η^°pHa 〇=C^&gt;c3H3 CH3 (E) [Effects of the Invention] When the liquid crystal alignment agent of the present invention is used, it can be carried out even if no crosslinking agent is added. A liquid crystal alignment film which is excellent in mechanical strength of film peeling and scratches during rubbing. When the liquid crystal alignment film is used, when the liquid crystal alignment energy is imparted by irradiation of polarized light, the voltage retention rate can be maintained at a high temperature. The liquid crystal display element having excellent density can be obtained. The liquid crystal alignment agent of the present invention protects a highly reactive primary or secondary aliphatic amine with a Boc group, so that it has high storage stability in a lacquer state. The polyimine precursors and polyimine contained in the liquid crystal alignment agent have high solubility in various organic solvents due to a Boc group having a high volume substituent, and are highly reactive by heating. Grade or 2 aliphatic amines • 15· 201033249 for intermolecular cross-linking reaction, thus forming excellent mechanical strength Polyimine film. Further, the diamine compound protected by the Boc group of the present invention can easily produce a polyimide precursor having a primary or secondary amine group protected by a Boc group by reacting with a tetracarboxylic acid derivative. Or a polyimine. [Form of the invention] The liquid crystal alignment agent of the invention is characterized by comprising a polyimine precursor having a 1 or 2 aliphatic amino group protected by a Boc group or a quinone imine thereof A polymer having a Boc group-protected grade 1 or 2 aliphatic amine group, having an aliphatic amine group of -NR3Boc (R3 is as defined in the above formula (1)), having a temperature of 150 ° C or higher a Boc-based protected grade 1 or 2 aliphatic amine-based polyimide precursor or a quinone imidized polymer thereof, which can be desorbed from the Boc group to form a reactive grade 1 or 2 fat that is not protected by the Boc group. An amine group. The resulting 1 or 2 aliphatic amine group reacts with a functional group present in the polyimide precursor or its oxime imidized polymer to form intermolecular crosslinks. Reaction with a carboxylic acid or an ester (the following formula (i)) and an acid dianhydride formed by a reverse reaction of polyglycine (The following formula (Π)), and the reaction with ruthenium (the following formula (iii) -16- 201033249 [Chem. 19]

(ϋ) It is presumed that the above-mentioned crosslinking reaction can enhance the liquid crystal alignment strength obtained by the present invention by the liquid crystal alignment liquid crystal alignment film of the present invention, and it is possible to carry out the film which does not cause film peeling and scratching when rubbing is performed. A method of imparting a liquid crystal alignment film to a liquid crystal alignment film, in addition to being known to be used separately, is a method of irradiating a polarized radiation to a polyimine liquid crystal alignment energy. The light alignment method that has been proposed is, for example, a method using a reaction, a method using a photocrosslinking reaction, and a method using a light separation method. The liquid crystal alignment agent and liquid crystal alignment film of the present invention are also suitable for use, in particular, a photoalignment method using a photodecomposition reaction. Further, in the photo-alignment method of light, a photopolymerization decomposition reaction portion which imparts a photoisomerization reaction to a film by a mechanical polyimine imprinting method which forms a film of a low molecular weight directional agent by light irradiation. For example, -17-201033249, in the photo-alignment method using a photodecomposition reaction of a polyalkyleneimine having a cyclobutane ring in the main chain, by performing an alignment treatment, a low molecular weight component having a maleic anhydride imide moiety can be produced (hereinafter Formula (xiii)). When a liquid crystal alignment film containing such a low molecular weight component is used for a liquid crystal display element, a low molecular weight component is eluted in the liquid crystal, and a voltage holding ratio of the liquid crystal display element is lowered and an ion density is increased, so that display characteristics of the liquid crystal display element may be changed. difference.

The liquid crystal alignment agent and the liquid crystal alignment film of the present invention can inhibit the low molecular weight of the polyimide precursor and the polyimine by the intermolecular three-dimensional crosslinking formed by the reaction of the above formulas (i) to (iU). And inhibiting the dissolution of low molecular weight components in the liquid crystal. Further, the maleic anhydride amide i produced by the photodecomposition reaction of the cyclobutane ring can be reacted with a primary or secondary aliphatic amine group formed by heating (the following formula (xiv)). This type of crosslinking reaction also inhibits the dissolution of low molecular weight components into the liquid crystal. It is estimated that a liquid crystal alignment film which imparts a liquid crystal alignment energy by a photo-alignment method can be used for a liquid crystal display element, and can maintain a high voltage holding ratio and a low ion density display characteristic at a high temperature. Liquid crystal display element. 18 - 201033249 [Chem. 22]

R1 〇

A--Ν F?2 R: (xiv) Further, even if a compound having two or more primary or secondary aliphatic amines is added to a solution of a polyimine precursor or a polyimine,

When a primary or secondary aliphatic amine is added to the quinone imine solution, a salt is formed with the carboxylic acid, or a quinone imidization reaction is carried out, or a ring opening reaction of the quinone ring is performed, thereby causing gelation of the polymer. Precipitation and molecular weight decrease, so it is difficult to settle the polymer solution for a long time. In contrast, the liquid crystal alignment agent of the present invention protects the first- or second-order aliphatic amine group with a Boc group. Therefore, when the liquid crystal alignment agent is stored in a solution state, it does not react with a functional group in the polymer, and a liquid crystal excellent in stability can be obtained. An aligning agent. Further, when a low molecular weight crosslinking agent is used, the low molecular crosslinking agent is sublimed upon firing in the liquid crystal alignment film forming process, so that an excessive amount is required to obtain a sufficient effect. However, when the amount is excessively added, the unreacted crosslinking agent remains in the film, and the voltage holding ratio and the ion density when used as a liquid crystal display element are deteriorated, so that good display may not be obtained. In addition, the sublimation cross-linking agent may contaminate the interior of the roaster. In contrast, the liquid crystal alignment agent of the present invention has an aliphatic amine having a crosslinking point in the polymer, so that the low molecular compound does not react and remains directly in the film, and the sublimate contaminates the baking furnace. From the above, it is known that the liquid crystal alignment agent of the present invention can be used, and the liquid crystal alignment film excellent in mechanical strength of film peeling and scratches does not occur when rubbed, and any alignment treatment is used when the liquid crystal alignment film is used. The method can obtain a liquid crystal display element which maintains a tube voltage holding ratio and a low ion density even at the barrel temperature. Further, a liquid crystal alignment agent excellent in stability can be obtained by protecting a 1 or 2 aliphatic amine group for a crosslinking point with a Boc group, and the present invention has been completed. The invention will be described in more detail below. A-[polyimine precursor and polyimine] The polyimine precursor of the present invention refers to a polymer capable of forming a polyimine by heating or a catalyst, such as polylysine , polyphthalate, polydecyl phthalate, polyisophthalimide. The polyamidene precursor is particularly preferably a polyamic acid or a polyamidamide in terms of ease of production and reaction efficiency of hydrazine imidization. Further, the polyimine of the present invention refers to a polymer obtained by imidating a polyimide precursor. The liquid crystal alignment agent of the present invention is a polyimide precursor containing a substituent represented by the following formula (1) or a quinone imidized polymer thereof. [化 23] 0 ch3 1 I —o--ch3 ch3 (1)

Ri R3

I I - A-C-N-

Wherein A is a single bond or a divalent organic group, and 1^, 2 and R3 are each independently a hydrogen atom or a carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 6 The price is organic. A monovalent organic group such as a monovalent hydrocarbon group, a hydroxyl group, -20-201033249 thiol group, a phosphate group, an ester group, a carboxyl group, a phosphate group, a thioester group, a nitro group, an organic oxy group, an organic decyl group, an organic group The viewpoint of the reactivity of the thio group or the quinone monovalent organic group with respect to the aliphatic amine is preferably a group. Specific examples of the monovalent hydrocarbon group are, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group or a decyl group; a cyclopentyl group, a cyclohexyl group; a bicycloalkyl group such as a dicyclohexyl group; a vinyl group; Alkenyl group such as 1-propenyl, 2-, isopropenyl, 1-methyl-2-propenyl, 1 or 2 or 3-butenyl φ; phenyl, xylyl, tolyl, biphenyl An aryl group such as a benzyl group, a phenylethyl group or a phenylcyclohexyl group. Some or all of the hydrogen atoms in the monovalent hydrocarbon group may be halogen atom, thiol group, phosphate group, ester group, carboxyl group, phosphate group, thioester group, nitro group, organooxy group, organodecyl group, organic sulfur Substituents such as alkyl, alkyl, cycloalkyl, bicycloalkyl, alkenyl, aryl, aralkyl, imidazolyl, pyrazolyl, alkoxycarbonylamino and the like. It is also a ring structure. Among them, a hydrogen atom on the nitrogen atom which is preferably a pyrrolyl group, an imidazolyl group or a pyrazolyl group Φ is a pyrrolyl group, an imidazolyl group or a pyrazolyl group is substituted. And when R2 is a high-volume structure, it will reduce the inverse of the cross-linking reaction, so the rule! And R2 is preferably a methyl group, an ethyl group, a propyl group, a butyl group or the like or a hydrogen atom, more preferably a hydrogen atom. When R3 is a high-volume structure, the reaction efficiency of the crosslinking reaction is lowered. R3 is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a hydrogen atom is preferably a hydrogen atom. When A is a divalent organic group, the structure is as shown in the following formula (12), amidino group or the like. a hydrocarbon of a valence, a t-al-cycloalkylene group, a hexenylnaphthyl group, a hydroxyl group, a fluorenyl group, a pyrrole group, etc., more preferably a B 〇c group should be an efficient alkyl group, and thus a sub- -21 - 201033249 - R5 - B - Rg - (12) In the formula (12), B is a divalent linking group, and R16 is independently a single bond or a carbon number of 1 to 20, preferably a divalent hydrocarbon group of 1 to 10. Specific examples of B are, for example, the following B-1 to B-14, but are not limited thereto.

[Chem. 25]

B-1 —CH2— B-2 R7 —CH— B-3 R7 ? Rs B -4 R/ B-5 Strict B-6 r8 1^8 B-7 〇B-8 —S — B-9 — N- Rg B-10 〇人 — B-11 〇—0 person B-12 〇人 I R10 B-13 〇AI B-14 〇V person? R10 Rio R11 -22- 201033249 The specifics of R6 and R! 6 in the formula (1 2 ) are as follows, but are not limited thereto. Methyl, 1,1-extended ethyl, 1,2-extended ethyl, 1,2-extended propyl, 1,3-extended propyl, 1,4-tert-butyl, 1,2-extended 1, 1, 2-pentyl, 1,2-extension, 1,2-extension, 1,2-extension, 2,3-butylene, 2,4-amyl Alkyl; 1,2-cyclopropyl, 1,2-cyclobutyl, 1,3-cyclobutyl, 1,2-cyclopentyl, 1,2-cyclobutyl, 1, a 2-ring-extension group, a 1,2-ring-extension group, etc.; a 1,1-vinyl group, a 1,2-vinyl group, a 1,2-vinyl group, a methyl group, a 1- Methyl-1,2-extended vinyl, 1,2-extended vinyl-1,1-extended ethyl, 1,2-extended vinyl-1,2-extended ethyl, 1,2-extended vinyl -1,2_propyl, 1,2-vinyl-1,3-propyl, 1,2-vinyl-1,4-butyl, 1.2-vinyl-1,2 - an extended alkenyl group such as a butyl group, a 1,2-vinyl group-1,2-exetylene group, a 1,2-vinyl group-1,2-anthracene group; an ethynyl group; Ethylene, ethynyl-1,1-extended ethyl, ethynyl-1,2-extended ethyl, ethynyl-1,2-extended propyl, ethynyl-1,3-propanyl, Ethylene-1,4-butylene, ethynyl-1,2- Butyl, ethynyl-1,2-exetylene φ, ethynyl-1,2-anthracenyl and the like alkynyl; 1,2-phenylene, 1,3 -phenyl, 1, 4-phenylene, 1,2-extended naphthyl, 1,4-naphthyl, 1,5-anthranyl, 2.3-anthranyl, 2,6-anthranyl, 3-phenyl-1 , 2-phenylene, 2,2'-di-phenylene, 2,2-dinaphthyl-1,1'-yl isocyanyl; 1,2·phenylphenylmethyl, 1,3- Stretching phenylmethyl, 1,4-phenylene methyl, 1,2-phenylene-1,1-extended ethyl, 1,2-phenylene-1,2-ethyl, 1, 2-phenylene-1,2-propanylpropyl, 1,2-phenylene-1,3-propanylpropyl, 1,2-phenylene-1,4-tert-butyl, 1,2- Phenyl-1,2-butylene, 1,2-phenylene-1,2-extended hexyl, methyl-1,2-phenyl extended methyl, methyl-1,3-extended Phenylmethyl, methyl-1,4-benzobenzene-23-201033249 A self-extension aryl group such as a methyl group and a difunctional hydrocarbon group formed by an alkyl group. Some or all of the above-mentioned divalent hydrocarbon groups may be halogen atoms, mercapto groups, thiol groups, pity ester groups, acetates, mercapto groups, pity groups, thioacetates, amide groups, nitro groups, organic groups. Oxygen, organic sand-based, organothio-branth, alkyl, cycloalkyl, bicycloalkyl, alkenyl, aryl, aryl, and the like. Again, these may be annular structures. When R6 and R16 are in a structure containing an aromatic ring or an alicyclic structure, the alignment of the liquid crystal may be lowered, so that R6 and R16 are preferably a single bond or an alkylene group, an alkenyl group or an alkynyl group having a carbon number of 1 to 10'. It is an alkylene group having 1 to 10 carbon atoms. It is preferable to use R6 and R, 6 or both of them as a single bond. In the structures represented by the above B-1 to B-14, 'Κ·7, Κ·8, Rs&gt;, Rio and Rn are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 2 carbon atoms. Wherein the monovalent hydrocarbon group is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a bicycloalkyl group such as a dicyclohexyl group; ; alkenyl group such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1 or 2 or 3-butenyl, hexenyl; An aryl group such as a tolyl group, a tolyl group, a biphenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylcyclohexyl group; and the like. Some or all of the hydrogen atoms in the monovalent hydrocarbon group may be a halogen atom, a hydroxyl group, a thiol group, a phosphate group, an ester group, a carboxyl group, a phosphate group, a thioester group, a decylamino group, a nitro group, an organooxy group, Substituted with an organic decyl group, an organic thio group, a decyl group, an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or the like. Again, these may be annular structures. R7, R8, R9, R1Q and Rn are aromatic rings or alicyclic structures, etc. --2433249. When the structure is formed, the alignment of the liquid crystal may be lowered and the solubility of the polymer may be lowered. Therefore, methyl or ethyl groups are preferred. An alkyl group such as a propyl group or a butyl group, or a hydrogen atom, more preferably a hydrogen atom. From the above, it is understood that the specific examples of the substituent of the first- or second-order aliphatic amine protected by the Boc group represented by the formula (1) are particularly preferably the structures of the following formulas (13) to (18).鲁 [化26] 1CH2)n—

H3C Chb NH 1~10 (13) -〇—(CH2)n—NH n= 1~10 (14) 1~10 ch3 (CH2)n-NH-n= 1~10 9 〇〇p °Λ°ΗΗ33 ~LNH-(CH2)n-NH-(CH3 fl7^-ΗΝ-^(ΟΗ2)η-ΝΗ-&lt;CH3 (i8) The liquid crystal alignment agent of the present invention is a polymer-containing terminal or a branch of a polymer A polyacid imide precursor having a substituent represented by the above formula (1) or a quinone imidized polymer thereof. In order to easily control the introduction amount of the substituent of the above formula (丨), a polymer branch is preferred. A polyimine precursor having a structural unit represented by the following formula (2), which is a substituent represented by the above formula (1), and a quinone imidized polymer thereof. -25- (2) 201033249 27] 〇〇r4o

Or4 NH—Y“NH (Z)b

(wherein, Xt is an organic group of (4 + a) valence, Y! is an organic group of (2 + b) valence, R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is the above formula (1) The structures are represented. a and b are each 0 to 4, preferably an integer of 0 to 2, a + b &gt; 0 ). The method for producing the polyimine precursor of the above formula (2) and the quinone imidized polymer thereof is preferably used, and the tetracarboxylic acid derivative and the diamine compound used for the raw material of the polyimide precursor are introduced. A raw material of the substituent represented by the above formula (1). Specifically, it is preferred to use a tetracarboxylic acid derivative represented by the following formulas (19) to (21) and a diamine compound represented by the following formula (22).

-26- 201033249 In the above formulas (19) to (21), R4 is an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group are, for example, methyl, ethyl, propyl, 2-propyl, butyl, t-butyl. Polyurethane esters increase the temperature at which the imidization is carried out according to the increase in the carbon number of the alkyl group. Therefore, R4 is preferably a methyl group or an ethyl group by the viewpoint of heat and imidization. Is a methyl group. Z is a substituent having a structure represented by the above formula (1), and a is an integer of 0 to 4. Parent 1 is the organic base of (4 + a) valence. (22) In the above formula (22), Z is an integer of 0 to 4 in the substituent 'b' having the structure represented by the above formula (1). 71 is an organic base of (2 + b) valence. The present invention can be carried out by using the tetracarboxylic acid derivative represented by the above formulas (19) to (21) and the diamine compound represented by the following formula (22), and the following formulas (23) to (25). The tetracarboxylic acid derivative represented by the following formula (26) and the diamine compound represented by the following formula (26) are mixed at these ratios to produce a polyimine precursor ', and a poly unit containing the structural unit represented by the above formula (2) is obtained. Anthraquinone precursor. [化30] Ο Ο

Ο Ο

0 201033249 In the above formulas (23) to (25), each of X and R4 is preferably as exemplified by the formulae (19) to (21). H2N-Y-NH2 (26) In the above formula (26), Y is a divalent organic group. In the above formulas (19) to (21) and the above formulas (23) to (25), the structures of X and Xi are not particularly limited. Specifically, for example, the configuration represented by the following X-1 to X-46. Further, these tetracarboxylic acid derivatives may be used in two or more types. However, in the above formulas (19) to (21), the valence of X i is changed by a of the substitution number of Z. In other words, the number of substitutions of Z can be such a structure that Xi is removed from any position in the structure represented by X -1 to X-46 described below.

[化32]

X-1 / \ X-2 CH is called 3 \ ch3 X-3 C h3ch3 / \ X-4 CH \ / CH 3ch3 3CH3 X-5 X-6 X-7 X-8 XX X-9 DC -28- 201033249 [化33]

X-10 xc X-11 iX X-12 mrc X-13 \ X-14 X-15 :=tc=: X-16 X-17 X-18 \x ch3 X-19 X-20 H3 ? X-21 V ch3 X-22 \x X-23 X-24 X-25 X X-26 XX X-27 x^a X-28 X-29 X-30 X-31 X-32 X-33 xrcc -29- 201033249 X-34 xr°xx Χ-35 χΛχ Χ-36 X-37 xAx Χ-38 F3CvCF3 Χ-39 \χ X-40 αχ Χ-41 αχ Χ-42 X-43 Χ-44 D^tC H3c Χ «45 h3c ^ X-46 In the above formula (22) and the above formula (26), the structures of γ and 1 are not particularly limited. Specifically, for example, the structure G represented by Y_1 to Y_i 00 described below. Further, two or more kinds of diamine compounds may be used. However, in the above formula (22), the valence of Y! is changed by the substitution number b of Z (b = 0 to 4). In other words, the number of substitutions of Z may be such a structure that the hydrogen atom is removed from any position in the structure represented by γ-1 to Y-100 described below. -30- 201033249

Yt -ο- Υ-2 XX Υ-3 χτα Y-4 Υ-5 Η3〇χτχχΗ3 Υ-6 -31 - 201033249 [化36] Y-7 Υ-8 Y-9 jaCH3 Υ-10 h3c Ch3 Υ-11 χχα Y-12 Cl Υ-13 〇-ch3 谷Υ-14 Y-15 h3c Υ-16 ch3 Υ-17 ^&lt;CH2 'ch2 Y-18 / ch2 Υ-19 Υ-20 Or\ Y -21 Υ-22 Υ-23 Y-24 &amp; Χ-25 Χ-26 H〇C CH3 X-27 h3c Υ-28 xra Υ-29 /OXJ Y-30 Υ-31 Υ-32 x/a Y- 33

-32- 201033249 [化37]

Y-34 Υ-35 αΑχ y-36 Y-37 H3c ch3 Υ-38 π乂CF3 α/α Υ-39 f3c cf3 Y-40 Η Υ-41 Υ-42 Y-43 Υ-44 Υ-45 Y- 46 Υ-47 Υ-43 Y-49 V Υ-50 6k Υ-51 XX

[化38]

Υ-52 ——(〇Η2)η— π=2 ～5 Y-53 CH3 —(CH2)2-C—(CH2)2— ch3 Υ-54 ch3 —(CH2)4-C—(CH2)3 — ch3 Y-55 ch3 ch3 1 1 3 —CH2—c—(CH2)2-C——(CH2)2—Υ-56 ch3 ch3 1 3 1 3 ~CH2-c (CH2)2-C (ch2) 3 Y-57 ch3 1 —(CH2)2-C —(c h2)5— H -33- 201033249 [化39] Y-58 Η3 —(CH2&gt;4-^—(ch2)5— Π Y-59 ~(CHjy-O—(CH2)2~〇~(CH^3—Υ-60 CH3 ch3 -(CH2)3-〒一Ο_Si-(CH2)3— ch3 ch3 Y-61 j〇tnJ Υ-62 Y -63 Υ-64 Y-65 V-66 Wrr Y-67 Χ-68 h3c ch3 X-69 h3c ch3 Υ-70 f3c cf3 OL0rAa0xr Y-71 n = 2 ～5 Υ-72 xx〇wia n = 2 ～5 Y-73 X^jO^^XXXX n=2 ～5 Υ-74 servant n = 2 ～5 Y-75 /〇—(C HA—., n=2 ～5

-34- 201033249 [化40]

Y-76 χτ η=5~19 Υ-77 CX η=5^19 Υ-78 ^OxMQ^Q-(CH2)n-CH3 Υ-79 η = 0 〜21 η = 0 〜21 Υ-80 k^ 〇KZ^O^(CH2)n&lt;:H3 Υ-81 k^'(&gt;0H^G^&lt;&gt;(CH2)n-CH3 η = 0 〜21 η = 0 〜21 Υ-82 0&quot;i^]HCHCH2&gt;n'cH3 n = 〇~21 Υ-83 ~)~^~~^-〇-(〇Η2)η-ch3 η = 0 〜21 Υ-84 ^^b-^)-Q^ (CH2)n-CH3 n = 0 to 21 Υ-85 ^^b_0~0_o_&lt;cH2)n^H3 η = 0 to 21 Υ-86 n = 0 to 21 Υ-87 n=0 to 21 Υ-88 Υ -89 201033249 [化41] Y-90 0 T 〇(〇H2)nCH3 n=0 〜21 Y-91 (CH2)nCH3 n=0~14 Y-92 ja°y°xx 00(CH2)nCH3 n=0 ～21 Y-93 O人0(CH2)nCH3 n=0~21 wch3~CH3 Y-94 Y-95 u Ηβη^ ο p^〇r -Q yo^ 〇6 wch3 wch3 H^Y^bH3 Y-96 h /3⁄4) Y-97 1 H3Cw&gt;—\ °~o~

[化42. Y-98 ό〇9 Y-99 0C Y-100

In the present invention, the substituent Z of the above formula (2) may be present in any part of the tetracarboxylic acid derivative or the diamine and may be one or more. In view of ease of manufacture and ease of handling of the monomer, it is preferred to use the diamine compound represented by the above formula (22). The polyimide precursor and the polyimine of the present invention are preferably a poly-36-201033249 quinone imide precursor having a structural unit represented by the following formula (3) and containing the following formula (7) The structural unit of the polyimine represented. [化 43] 〇 〇 -or4

X r4〇- (3) -NH-Y2-NH-

〇 〇 &lt;Z)&lt; In the formula (3), X is a tetravalent organic group, and γ2 is an organic group of (2 + c) valence. 'R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z is a structure represented by the above formula (1). c is an integer from 1 to 4, preferably from 舄 to 2. [化44]

In the formula (7), X, Y2, Z and C have the same meanings as in the above formula (3). a polyimide precursor or a polyimide containing a structural unit of the above formulas (3) and (7), wherein the tetracarboxylic acid derivative represented by the above formulas (23) to (25) is mixed at an arbitrary ratio and The diamine compound represented by the following formula (27) is obtained by reacting the diamine compound represented by the above formula (26). -37- 201033249 [Chem. 45]

H2N - 丫2 - NH2 (27) In the formula (27), Y2, Z, and c have the same meanings as the above formulas (3) and (7). Specifically, for example, the configuration represented by Υ-1 to γ_100 is as described above. Further, two or more kinds of diamine compounds may be used. However, in the above formula (27), the valence of γ2 is changed by c of the substitution number of Ζ. In other words, the structure in which the hydrogen atom is removed from any position in the structure represented by Υ-1 to Υ·1〇〇 can be used as the structure of Υ2, and the use of biphenyl, cyclohexyl, or steroid-free is used. a high-volume branched diamine compound having a carbon number of 10 or more and a high volume branched diamine compound such as a fluoroalkyl group, which comprises a polyamine imine precursor of an aromatic amine group or a polyimine. A liquid crystal alignment film having good liquid crystal alignment and excellent mechanical properties is obtained. The liquid crystal alignment agent of the present invention preferably contains a polyimine precursor containing a structural unit represented by the following formula (4) or a polyimine containing a structural unit represented by the following formula (9). (Ζ),

201033249 (wherein X, R4, Z and c are the same meanings as in the above formula (3), and r5 is a single bond or a divalent organic group having an aromatic group).

(wherein, X, Z, R5 and c have the same meanings as in the above formula (4)). When the polymer obtained by the present invention has a high linearity, a liquid crystal alignment film having a good liquid crystal alignment property can be obtained. Therefore, the diamine compound containing the substituent Z is more preferably a diamine compound represented by the following formulas (28) to (44) and the following formulas (58) to (61). In the equation, 'Z is a structure represented by the above formula (?1), C is an integer of 1 to 4, and d and e are integers of 1 to 2. (Z)c H2N&lt;^h2 (30) (Z)c &lt;^)c H2N-^^-NH2 (28) H2N-h^ (29) IMH2 [Chem. 49]

(Z)c HsN

H2 (31)

(33) -39- 201033249 [Chem. 50] (Z)d

IZ )c K NH2(34) H2N^3~(CH2)(^-NHi35) n = 3~5 [化51] &lt;Z)d «Z)e (CH2)n_v3-NH2(36^&gt; H2N ^^ , (ch2)

A ^nh2(37) 3-5 2~5 10 [Chem. 52]

e NH〇(38) H2N (Z )d Ο O (Z)e CH2)n-^. 2~5 丨~^~NH2(39) (Z )c :2~5 (CH2)nq i = 2 ~5 (41) [Chem. 54] H2N[化55] (Z)d

P-(CH2)n· =2-5 (Z)e &lt;Z) 玛(42) h2n 10

,N' NH2 (43) (44) Η2Ν^ ^NH2 40- 201033249 [Chem. 56]

The polymer backbone of the present invention is a polyimine film having excellent mechanical strength when it is straight. Therefore, the polyimide precursor of the present invention and the polyimine are more preferably, and contain the following formula (5). The polyimine precursor of the structural unit represented, and the polyimine containing the structural unit represented by the following formula (11). [化57]

U )c

C〇〇r4 (5)

CO—x—CO—NH

I coor4 (wherein, X, R4, Z and c are the same meanings as the above formula (3) -41 - 201033249

(li) (wherein, X, R4, Z and c are the same meanings as in the above formula (3) b. [Specific diamine compound] The diamine compound of the raw material for producing a polyimide precursor in the present invention Jiaru, a diamine compound of the following formula (A) to (F).

H2N NH NH,

(A) H2N

CH. HaOXthHa0 丫5 ,(CH2)3-NH (C)

H3C CH3 -Chb NH2 (B) H2N^VnH2 \ch2)3hsih c/o HaC^Chb

G &gt;0 HN NH H2N-^HvJH2 (D) H2N-^^NH2

CH, (E)

-42-201033249 bl. [Production of Diamine Compound] The production method of the specific diamine compound represented by the above formulas (A) to (E) will be described below, but the present invention is not limited thereto. First, the diamine compound of the above formula (A) can be produced, for example, by using 2-cyano-4-nitroaniline of the following formula (45) as a starting material and by an intermediate represented by the following formula (iv).

[60]

CN °2N-&lt;(~/~NH2 (45) [Chem. 61]

CN 〇2N-^^-NH2~~^〇2hh^^-NH2—- 〇^3 -ΝΗ &lt;\&gt;ΝΗ2 —

First, the 2-cyano-4-nitroaniline of the above formula (45) is dissolved in an organic solvent. The organic solvent to be used may be an organic solvent capable of dissolving 2-cyano-4-nitroaniline but not decomposed by the reducing agent added thereafter, and is not particularly limited, and is preferably dehydrated tetrahydrofuran (THF). ). After the obtained 2-cyano-4-nitroaniline solution is cooled to -40 ° C to 70 ° C, preferably - 20 ° C to 20 ° C, the reducing agent is added while stirring the reaction solution. When the reducing agent is a powder, it is preferred to directly add the reaction solution, and when the reducing agent is a solution, it is preferably added as a dropping liquid. The reducing agent is, for example, borane, borane complex, sodium borohydride, lithium aluminum hydride or the like, preferably a borane-THF complex. Add -43- 201033249 After the reducing agent is cooled, the reaction solution is stirred for 30 minutes to 4 hours, preferably 1 to 2 hours. Thereafter, it is stirred at room temperature for 12 to 72 hours, preferably 24 to 48 hours. After the completion of the reaction, 1 to 2 Torr of the inorganic acid is added to make the reaction solution acidic. The inorganic acid is, for example, hydrochloric acid, hydrogen fluoride, brominated hydrogen acid, iodinated hydrogen acid, phosphoric acid, nitric acid, sulfuric acid, boric acid or the like, more preferably hydrochloric acid. After the addition of the inorganic acid, the mixture is stirred at room temperature for 1 to 2 hours, and then the reaction solution is cooled to 〇 to 10 ° C, and then 1 to 2 Torr of an aqueous solution of an inorganic base is added to make the reaction solution alkaline. An aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate or potassium hydrogencarbonate is preferably sodium hydroxide. After the reaction solution is made alkaline, an organic solvent is added for extraction. The organic solvent for extraction is preferably a halogen organic solvent, more preferably methylene chloride. The obtained organic layer was washed with pure water or saturated brine and dried with a drying agent. The desiccant is preferably sodium sulfate or magnesium sulfate. The resulting organic layer has a drying time of 4 to 24 hours, preferably 12 to 24 hours. After the desiccant is removed, the solvent is distilled off from the obtained filtrate to obtain a compound represented by the following formula (46). The obtained compound can be used in the next reaction without purification, but can be purified by various methods. The purification method is, for example, tannin column chromatography, recrystallization, washing with an organic solvent, etc., but recrystallization is more preferable in terms of ease of operation and improvement of purification efficiency. The organic solvent for recrystallization may be an organic solvent which can recrystallize the following formula (46), and is not limited to the type, and may be recrystallized using two or more kinds of mixed solvents. [化 62]

NH2 02N NH2 (46) 201033249 Next, a method of producing the following formula (47) from the compound represented by the above formula (46) will be explained. [化63]

^-NH 〇〇2N~^NH2 (47) First, the compound represented by the above formula (46) is dissolved in an organic solvent, and after adding di-tert-butyl dicarbonate, the reaction temperature is -10 ° C to 40 The reaction is carried out by stirring at °C to 20 ° C for 12 to 48 hours, preferably 20 to 4 hours. The organic solvent used in the reaction may be one which is capable of dissolving the compound of the above formula (46) and which does not react with di-tert-butyl dicarbonate, and is not limited to the type 'but preferably dichloromethane or tetrahydrofuran. Further, in order to carry out the reaction more efficiently, φ can be added with an organic base such as triethylamine or pyridine. The amount of addition is preferably from 1 to 2 mole parts based on the compound of the above formula (46). After completion of the reaction, an organic solvent, pure water or saturated brine is added for extraction, and a desiccant is added to the obtained organic layer to dry. The organic solvent for extraction may be one which does not mix with water, and is not limited to the type, but dichloromethane is preferred. Further, water or saturated brine may be added to the reaction solution for extraction. The desiccant is preferably sodium sulfate or magnesium sulfate. The drying time of the resulting organic layer is from 4 to 24 hours, preferably from 12 to 24 hours. After the desiccant is removed, the solvent is distilled off from the obtained filtrate to obtain a compound represented by the above formula (47). The obtained compound of -45 to 201033249 can be used in the next reaction without purification, but it is preferably purified by various methods. The purification method is, for example, 'gel column chromatography, recrystallization, washing with an organic solvent, etc., but recrystallization is preferred in terms of ease of operation and improvement of purification efficiency. The organic solvent to be recrystallized may be an organic solvent which can recrystallize the following formula (47), and is not limited to the type, and may be recrystallized from a mixed solvent of two or more kinds. Next, a method of producing a diamine compound represented by the following formula (A) from the compound represented by the above formula (47) will be explained. [化 64]

First, the compound represented by the above formula (47) is dissolved in an organic solvent. The organic solvent to be used may be known, and is not limited to the kind thereof. In order to carry out the reaction more efficiently, methanol, ethanol, 2-propanol, tetrahydrofuran or 1,4-dioxane is preferred, and methanol or ethanol is more preferred. After dissolving the compound represented by the above formula (47) in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, and then the catalyst is added, and the inside of the reaction vessel is replaced with hydrogen. The catalyst is, for example, palladium carbon, crude platinum carbon, uranium oxide or the like, but in order to suppress the decomposition reaction of the benzyl group, platinum oxide is more preferred. 〇 ° C to l ° ° C, preferably 10 to 6 (TC stirred reaction mixture 〇 to 48 hours, preferably 15 to 30 hours. After the reaction is completed, the catalyst is removed, and the organic solvent is distilled off. The diamine compound of the present invention represented by the above formula (A) can be obtained. The obtained compound cannot be polymerized without being purified, and a polymer having a high molecular weight cannot be obtained. Therefore, it is preferably purified by various methods. The purification method is, for example, 'gelatin column chromatography, recrystallization, washing with an organic solvent, etc.', but recrystallization is preferred in terms of ease of operation and purification efficiency. The organic solvent used for recrystallization may be the following formula ( The organic solvent for recrystallizing the diamine of A) is not limited to the type, and may be recrystallized by a mixed solvent of two or more kinds. The following is a method for producing a diamine compound of the above formulas (B) and (c). The diamine compound of the above formula (B) and (C) can be produced, for example, by using propynamide of the following formula (48) as a starting material, and by an intermediate represented by the following formulas (v) to (vi). [化65] λνη2 (48) [Chem. 66]

JH H3CCH3

-NH ΝΗ 2 〇2N-\_^-NH2-〇2N-\_^~NH2 (v) [化67] γ-ΝΗ ΝΗ, 〇;3! ^ΝΗ ΗΝ-Ρ 〇Η^—► 〇2Ν〇 ΝΗ2—&quot; 〇2N-C5hmH2 (vi) ΗΝ-^ generous> ^CCH3 °a3 -47- 201033249 The above diamines (B) and (C) are each using the following formulas (49) and (50). In addition to the manufacture of the iodinated aryl group, the others can be produced in the same manner. Further, a substitution position of an iodine group of the following formulas (49) and (50); a compound substituted with a bromo group or a trifluoromethylsulfonyl group may be used, but an aryl iodide is preferred from the viewpoint of reactivity. [化68] o2n

H2 (49)

[化69] o2n

Next, a method of producing Boc-propargylamine of the following formula (51) from the propynylamine of the above formula (48) will be explained.

HN-&lt;3 3 (51) Propynylamine is dissolved in an organic solvent, and an organic base is added. The organic solvent for the reaction may be any one which is capable of dissolving propargylamine but not reacting with di-tirt-butyl dicarbonate to be added thereto, and is preferably of a methylene chloride. The purpose of adding an organic base is to enhance the nucleophilicity of the amine group, and more preferably it is tri-48-201033249 ethylamine or pyridine. The reaction solution is allowed to drip di-tert-butyl dicarbonate into the reaction solution at _5 ° C to 40 ° C, preferably 0 ° C to 20 ° C. When the drip is too fast, the reaction will be carried out violently. Therefore, the dripping time is preferably from 1 Torr to 1 hour. Further, the dropping speed is changed depending on the amount of di-tert-butyl dicarbonate added. After the completion of the dropping, the mixture is stirred for 1 to 1 hour, preferably 2 to 4 hours, and water or a saturated saline solution and an organic solvent are added to the reaction solution for extraction. The organic solvent for extraction may be one which does not mix water, and is not limited to the φ type, but it is preferably the same as the one used for the reaction. The resulting organic layer was extracted by drying with a drying agent. The desiccant is preferably sodium sulfate or magnesium sulfate. The resulting organic layer has a drying time of 4 to 24 hours, preferably 12 to 24 hours. After the desiccant is removed, the solvent is distilled off from the obtained filtrate to obtain a compound represented by the above formula (5 1 ). The obtained compound can be used in the next reaction without purification, but it is preferably purified by various methods. The purification method is, for example, sand column chromatography, recrystallization, washing with an organic solvent, etc., but recrystallization is more preferable in terms of ease of operation and improvement of purification efficiency. The organic solvent to be recrystallized may be an organic solvent which can recrystallize the following formula (51), and is not limited to the type, and may be recrystallized using a mixed solvent of two or more kinds. Next, a method of producing the compound represented by the following formula (52) will be explained using a compound represented by the above formula (51). [化71]

-49- 201033249 The compound represented by the above formula (52) can be produced by a Sonogashira coupling reaction of the Boc-propargylamine of the above formula (51) with the aryl halide represented by the above formula (49). . The aryl iodide, the palladium catalyst, and the copper catalyst represented by the above formula (49) are added and dissolved in an organic solvent. The palladium catalyst is preferably bis(triphenylphosphine) pin (II) dichloride, and the amount thereof is preferably 0.05 to 1.0 mol% relative to the iodine group of the aryl iodide, more preferably 01 to 0.5 mol. %. The amount of the copper catalyst is preferably 〇.05 to 1.0 mol%, more preferably Ο. to 〇5 mol%, relative to the iodine group of the aryl halide. The base is preferably triethylamine or diethylamine. The amount thereof is preferably from 1 to 3 mole parts, more preferably from 1 to 2 mole parts, based on the iodine group of the aryl iodide. The organic solvent for the reaction may be one which is capable of dissolving the aryl iodide but does not react with various reagents added thereto, and is not limited to the type ', but preferably hydrazine or dimethylformamide. After stirring the above reaction solution at 〇 ° C to 30 ° C, preferably 0 ° C to 20 ° C for 5 to 30 minutes, the Boc-propargylamine of the above formula (51) is added, and the mixture is stirred for 2 to 12 hours. Preferably, it is 4 to 10 hours. The amount of Boc-propargylamine added is preferably from 1 to 2 mole parts, more preferably from 1.20 to 1.50 mole parts, relative to the iodine group of the aryl iodide. An organic solvent and an acidic aqueous solution are added to the reaction solution for extraction. The organic solvent to be extracted may be one which does not mix water, and is not limited to the type, but is preferably ethyl acetate, dichloromethane, chloroform or 1,2-dichloroethane. The acidic aqueous solution is preferably an aqueous solution of ammonium chloride, hydrochloric acid, acetic acid or formic acid. When the acidity is too high, Boc may be detached, so that an aqueous solution of ammonium chloride is more preferable. The concentration of the acid -50 to 201033249 solution is preferably from 0.5 to 2 mol/L, more preferably from 1 to 1.5 mol/L. The obtained organic layer was washed with an acidic aqueous solution several times, and then dried with a drying agent. The desiccant is preferably sodium sulfate or magnesium sulfate. The drying time of the obtained organic layer is 4 to 24 hours, preferably 12 to 24 hours. After the desiccant is removed, the solvent is distilled off from the obtained filtrate to obtain a compound represented by the above formula (52). The obtained compound can be used in the next reaction without purification, but it is preferably purified by various methods. The purification method is, for example, tannin column chromatography, recrystallization, φ washing with an organic solvent, etc., but the operation is simple and the purification efficiency is improved to recrystallization. The organic solvent to be recrystallized may be an organic solvent which can recrystallize the above formula (52), and is not limited to the type, and may be recrystallized using two or more kinds of mixed solvents. The diamine compound of the present invention represented by the following formula (B) can be produced by a hydrogenation reaction of the compound represented by the above formula (52). [化72] h3c ch3 3

H2N

NH (B) The compound represented by the above formula (52) is dissolved in an organic solvent. The organic solvent to be used may be a known one, and is not limited to its kind, but in order to promote the reaction more efficiently, methanol, ethanol, 2-propanol, tetrahydrofuran, 1,4-dioxane, more preferably methanol, Ethanol. After dissolving the compound represented by the above formula (52) in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, and then the catalyst is added, and the inside of the reaction vessel is replaced with hydrogen. The catalyst is, for example, palladium carbon, crude platinum -51 - 201033249 carbon, sodium oxide, etc., but the reaction efficiency is better as palladium carbon. The reaction mixture is stirred at 10 to rc, preferably 10 to 6 ° C for 15 to 72 hours, preferably 24 to 48 hours. After the reaction is completed, the catalyst is removed, and the organic solvent is distilled off to obtain the above formula (B). The diamine compound of the present invention represented by the present invention. When the obtained compound is not highly purified, polymerization cannot be carried out, and a polymer having a high molecular weight cannot be obtained. Therefore, it is preferably purified by various methods. The purification method is, for example, a silica gel column chromatography. Recrystallization, washing with an organic solvent, etc., but recrystallization is preferred in terms of ease of handling and purification efficiency. The organic solvent used for recrystallization can recrystallize the diamine represented by the above formula (B). The organic solvent is not limited to the type, and may be recrystallized by using two or more kinds of mixed solvents. The following are the methods for producing the diamine compound of the above formulas (D) and (E), but are not limited thereto. The diamine compound of D) and (E) can be, for example, 2-amino-4-nitroaniline of the following formula (53) and an amino acid compound of the following formula (54) as a starting material, via the following formula ( Vii) The intermediates are represented by the following formula ( The amino acid compound of 54) is a compound in which the amine group of the amino acid is protected by Boc. The diamine compounds of the above formulas (D) and (E) may each be a Boc group using an amine group of glycine and histidine. The protected amino acid compound is produced. Further, other amino acids can be produced by the same manufacturing method. [Chem. 73] 201033249 [Chem. 74] 9 R12 hch3 H〇J--NT^O八CH3(54)

Rl3H

[化75]

By reacting 2-amino-4-nitroaniline of the above formula (53) with an amino acid compound represented by the above formula (54), a compound represented by the following formula (55) can be obtained.

The amine group at the 1-position of 2-amino-4-nitroaniline is affected by the presence of a nitro group at the 4-position to lower the nucleophilicity. Therefore, the compound represented by the above formula (55) can be produced by preferentially reacting the amine group at the 2-position with the decanoic acid of the amino acid 201033249 compound. When an excess of the amino acid compound is added, 'the amine bond is formed with the amine group at the 4- position. Therefore, the amount of the amino acid compound added is preferably 0.9 to 1.2 times the molar amount relative to the 2-amino-4-nitroaniline. The compound represented by the above formula (55) can be produced by a condensation reaction of an amine group at the 2-position of 2-amino-4-nitroaniline with a carboxylic acid of the amino acid compound of the above formula (54). The method of preparing the amine group and the carboxylic acid may be a known method, and the type thereof is not limited. However, it is preferred to use a method of mixing a dianhydride or a method of using a condensing agent in the production of the diamine compound of the present invention. The method of using a mixed acid anhydride, for example, after reacting a carboxylic acid with an acid halide or an acid derivative in an organic solvent at -4 ° C to 40 ° C ', preferably - 20 ° C to 5 ° C in the presence of a base 'In the organic solvent to -40. (: to 40 ° C, preferably -20 ° C to 5 ° C, the resulting mixed acid anhydride is reacted with 2-amino-4-nitroaniline. The organic solvent for the reaction may be such that it can dissolve the above formula (54). The amino acid compound represented by the reaction, but not reacting with the respective reagents for the reaction, is not limited to the type, but is preferably dehydrated chloroform, dichloromethane or tetrahydrofurfuryl, relative to the amine. The solubility of the carboxylic acid compound is more preferably tetrahydrofuran. The base for the reaction is preferably a tertiary amine, more preferably pyridine, triethylamine, dimethylaminopyridine or N-methylmorpholine. When it is too much, it is difficult to remove, so it is preferably 2 to 4 times moles relative to 2-amino-4-nitroaniline. The acid halide and acid derivative are preferably trimethyl ethane chloride, p-toluene. Sulfonium chloride, methanesulfonium chloride, ethyl chloroformate, isobutyl chloroformate. The acid halide and the acid derivative are preferably added in an amount of 1.5 to 0.5% by weight based on 2-amino-4-nitroaniline. 2 times Mo. -54- 201033249 The method of using a condensing agent is, in the presence of a condensing agent, a base and an organic solvent, 〇 ° C to 150 ° C, preferably 0 ° C to loot: 2 The amino-4-nitroaniline is reacted with the amino acid compound for 30 minutes to 24 hours, preferably 3 to 15 hours. The above condensing agent may use triphenylphosphite, dicyclohexylcarbodiimide. , 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, hydrazine, Ν'-carbon quinone diimidazole, dimethoxy-1,3,5-three Zinylmethylmorpholine _, 〇-benzotriazol-1-yl)-^?^,^^-tetramethylurea, tetrafluoroborate, Ο-benzotriazol-1-yl) -Ν,Ν,Ν',Ν'-tetramethylurea key hexafluorophosphate, (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonic acid diphenyl ester, and the like. The amount of the condensing agent added is preferably 2 to 3 times moles relative to the amino acid compound. As the base, a tertiary amine such as pyridine or triethylamine can be used. When the amount of the base added is too large, it is difficult to remove, and when it is too small, the molecular weight is lowered, so it is preferably 2 to 4 times moles relative to 2-amino-4-nitroaniline. Further, in the above method using a condensing agent, the Lewis acid can be added to carry out the reaction efficiently. Preferably, the Lewis acid is φ lithium halide such as lithium chloride or lithium bromide. The Lewis acid is preferably added in an amount of from 0 to 1.0 moles per mole of 2-amino-4-nitroaniline. Preferably, the above two methods are carried out by removing the precipitate from the obtained reaction solution, adding an acidic or basic aqueous solution and an organic solvent, and extracting and removing the acid halide or the acid derivative, the condensing agent and the base. The acidic aqueous solution is preferably an aqueous solution of hydrochloric acid, acetic acid, formic acid or ammonium chloride. The aqueous alkaline solution is preferably an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate or potassium carbonate. The organic solvent for extraction may be one in which no content is precipitated in the reaction solution, and the water is not mixed, and is not limited to the type, but is preferably ethyl acetate, dichloromethane, chlorine-55-201033249, 1 , 2-dichloroethane. The obtained organic layer was washed several times with the above acidic aqueous solution or the above aqueous alkaline solution, and then dried with a drying agent. The desiccant is preferably sodium sulfate or magnesium sulfate. The drying time of the obtained organic layer is 4 to 24 hours, preferably 12 to 24 hours. After the desiccant is removed, the solvent is distilled off from the obtained filtrate to obtain a compound represented by the above formula (55). The obtained compound can be used in the next reaction without purification, but it is preferably purified by various methods. The purification method is, for example, silica gel column chromatography, recrystallization, washing with an organic solvent, etc., but the ease of operation is 'improving the purification efficiency and recrystallization. The organic solvent used for the recrystallization may be an organic solvent which is capable of recrystallizing the compound represented by the above formula (55), and may be recrystallized using a mixed solvent of two or more kinds. The compound represented by the above formula (55) can be produced by a hydrogenation reaction to produce a diamine compound represented by the following formula (56). [化77]

Rc3i^~Ri3NHH2N-^^-NH2 (56) First, the compound represented by the above formula (55) is dissolved in an organic solvent. The organic solvent to be used may be a known one, and is not limited to its kind, but in order to carry out the reaction more efficiently, methanol, ethanol, 2-propanol, tetrahydrofuro-56-201033249, and 1,4-dioxin are preferred. The alkane is more preferably methanol or ethanol. After dissolving the compound represented by the above formula (55) in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, and then the catalyst is added, and the inside of the reaction vessel is replaced with hydrogen. The catalyst is, for example, palladium carbon, crude platinum carbon, platinum oxide or the like, but the reaction efficiency is preferably palladium carbon. The reaction mixture is stirred at 100 ° C, preferably 10 to 60 ° C, for 15 to 72 hours, preferably 24 to 48 hours. After the completion of the reaction, the catalyst is removed, and the organic solvent is distilled off to obtain the diamine compound φ of the present invention represented by the above formula (56). When the obtained compound is not highly purified, the polymerization reaction cannot be carried out, and a polymer having a high molecular weight cannot be obtained. Therefore, it is preferred to carry out purification by various methods. The purification method is, for example, tannin column chromatography, recrystallization, washing with an organic solvent, etc., but recrystallization is preferred in terms of ease of operation and improvement of purification efficiency. The organic solvent to be used for the recrystallization may be an organic solvent capable of recrystallizing the diamine represented by the following formula (56), and may be recrystallized using two or more kinds of mixed solvents. 〇c. [Production of Polyimine Precursor and Polyimine] The polyamine imide precursor of the present invention and a polyimide, a diamine compound having a substituent represented by the formula (1) and having At least one compound (hereinafter also referred to as a specific monomer) selected from the group consisting of the substituent tetracarboxylic acid derivatives represented by the formula (1) is produced. More specifically, it is produced by using the tetracarboxylic acid derivative represented by the above formula (19) to formula (21) and/or the diamine compound represented by the formula (22). Among them, the specific monomer is preferably a diamine compound having a substituent represented by the above formula (1). When the polyimine precursor of the present invention and the polyimine are produced, the raw material mono-57-201033249 can be used as a tetracarboxylic acid derivative other than the specific monomer (for example, the above formula (23) to formula (25) The tetracarboxylic acid derivative shown) and/or one of the amine compounds other than the specific monomer (for example, the diamine compound represented by the above formula (26)). At this time, the specific monomer used in the raw material monomer is preferably used in an amount of 2 to 1 mol%, and more preferably 2 to 60 mol%, more preferably 2 to 50 mol%, particularly preferably 2 to 30% of the mole. In the present invention, the raw material single system refers to a polycarboxylic acid imide precursor of the present invention and a tetracarboxylic acid derivative and a diamine compound for polyimine. However, the tetracarboxylic acid derivative and/or diamine compound used in the present invention comprises a specific monomer cl. (manufacturing polyglycine). The polyamine acid precursor of the polyimide precursor can be derived from tetracarboxylic dianhydride and The diamine compound is produced (the following formula (viii)), and the tetracarboxylic dianhydride and/or the diamine compound contains a specific monomer.

[化78]

COOH I , a HNOC - X - CONHY - IL COOH "n (viii) When producing a polyimide precursor, the tetracarboxylic dianhydride and the diamine compound are preferably present in an organic solvent at -20 ° C The reaction is carried out at 140 ° C, preferably at 〇 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 12 hours. The solvent used for the production of the polylysine of the above formula (viii) is preferably N,N-dimethylformamide or N-methyl-2 in terms of solubility of the monomer and poly-58-201033249. - Pyrrolidone, γ-butyrolactone, and the like may be used alone or in combination of two or more. When the concentration is too high, the polymer is easily precipitated, and when the concentration is too low, the molecular weight cannot be increased. Therefore, the total amount of the reaction solution of the tetracarboxylic dianhydride and the diamine compound is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. The polylysine obtained as described above may be used as a liquid crystal alignment agent of the present invention, but when the liquid crystal alignment agent does not contain a solvent for polymerization, the polymer may be recovered as a solid, and then used as the polyamine of the present invention. For acid use. The polymer can be recovered by injecting a weak solvent while sufficiently stirring the reaction solution to precipitate a polymer. After several times of precipitation, it is washed with a weak solvent, and then dried at room temperature or by heating to obtain a purified polyamino acid powder. The weak solvent is not particularly limited, and may be water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like. C2. (Manufacture of Polyurethane) φ Polyurethane can be produced by a known production method, specifically, for example, the methods (a) to (c) below, but are not limited thereto. (a) When polyurethane is produced from polylysine [Chem. 79] "COOH • COOR3 &quot; | -HNOC-X-CONH-Ύ-一-- | -HNOC-X-CONH-Y--( Ix) 1 L COOH η | - COOR3 - η -59- 201033249 The polyperurethane of the present invention can be obtained by esterifying the above polyamine of the present invention (formula (ix) above). Specifically, the polyglycolic acid and the esterifying agent are reacted for 30 minutes to 24 hours, preferably 1 hour, in an organic solvent at -20 ° C to 140 ° C, preferably at 〇 ° C to 50 ° C. It will take 4 hours. The esterifying agent is preferably one which is easily removed by purification, such as hydrazine, hydrazine-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide neopentyl butyl acetal, N,N-dimethylformamide di-t-butyl Acetal, 1-methyl-3-P-tolyltriazene, i•ethyl-3-P-tolyltriazene, propyl-3-p-tolyltriazene, and the like. The amount of the esterifying agent to be added is preferably from 2 to 6 mol equivalents per 1 mol of the repeating unit of the polyamino acid. The solvent for the polyphthalate of the above formula (ix) is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidinium, and the solubility of the monomer and the polymer. 7-butyrolactone may be used alone or in combination of two or more. When the concentration at the time of manufacture is too high, the polymer is easily precipitated, and when the concentration is too low, the molecular weight cannot be increased. Therefore, the total amount in the reaction liquid of the polyamic acid and the esterifying agent is preferably from 1 to 30% by mass, more preferably from 5 to 20 0 quality. /〇. (b) When a polyglycolate formed from an acid chloride or a diamine compound is produced [Chem. 80]

201033249 Polyamphanes can be produced from acid chlorides and diamine compounds (Formula (X) above). The acid chloride and/or diamine compound of the present invention contains a specific monomer. Specifically, the acid chloride and the diamine compound are reacted in an amount of from -20 ° C to 140 ° C in an alkali and an organic solvent, preferably from 〇 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 It will take 4 hours. As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but in order to stabilize the reaction, φ is preferably pyridine. When the amount of the base added is too large, it is difficult to remove, and when it is too small, the amount of the molecule is lowered, so that it is preferably 2 to 4 times moles relative to the acid chloride. The solvent for the polyglycolate of the above formula (X) is preferably N-methyl-2-pyrrolidone or 7-butyrolactone in terms of solubility of the monomer and the polymer, and the like may be one or two. More than one kind of mixture is used. When the concentration at the time of manufacture is too high, the polymer is easily precipitated, and when the concentration is too low, the molecular weight cannot be increased. Therefore, the total amount in the reaction liquid of the acid chloride and the diamine compound is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. %. Further, in order to prevent the hydrolysis of the acid chloride, the solvent for producing the phthalocyanine ester is preferably dehydrated as much as possible, and it is preferable to prevent the outside air from being mixed in the nitrogen atmosphere. (c) Polyurethane ester formed from dialkyl ester dicarboxylic acid and diamine compound [U.S.] U U HO-^ /L〇R3 r3o

Η〗 Ν Υ Υ ΝΗ 2 ο ο COOR3 -HNOC—i—CONHY—(xi) I 3 L COOR3 Jn -61 - 201033249 Polyphthalate can condense dialkyl ester dicarboxylic acid and condensate by condensing agent The amine compound is obtained (the above formula (xi)). In the present invention, the dialkyl ester dissid acid and/or the diamine compound contains a specific monomer. Specifically, the dialkyl ester dicarboxylic acid and the diamine compound are reacted for 30 minutes to 24 hours in the presence of a condensing agent, a base and an organic solvent to 140 ° C, preferably 〇 ° C to 10 ° C. It is preferably from 3 to 15 hours. As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride can be used. ,Ν'-Carbonium diimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine, 〇-(benzotriazol-1-yl)-zabi: ^',:^ -tetramethylurea, tetrafluoroborate, 0-(benzotriazol-1-yl)-indole, hydrazine, hydrazine, Ν'-tetramethylurea hexafluorophosphate, (2,3- Diphenyl 2-dihydro-2-thio-3-benzoxazolyl)phosphonate and the like. The amount of the condensing agent added is preferably 2 to 3 moles per mole of the dialkyl ester dicarboxylic acid. As the base, a tertiary amine such as pyridine or triethylamine can be used. When the amount of the base added is too large, it is difficult to remove, and when it is too small, the molecular weight is lowered, so that it is preferably 2 to 4 times moles relative to the diamine oxime component. Further, when the Lewis acid is added to the above reaction, the reaction can be carried out efficiently. The Lewis acid is preferably lithium chloride or lithium bromide. The Lewis acid is preferably added in an amount of from 1.0 to 2 moles per mole of the diamine component. In the method for producing the above three kinds of polyphthalate, a production method of (a) and (b) is particularly preferable in order to obtain a high molecular weight polyglycolate. From the polyphthalate solution obtained above, the polymer can be precipitated by injecting a weak solvent while stirring well. After several times of precipitation, it is washed with a weak solvent, and the mixture is dried at room temperature or by heating to obtain a purified polyfluorene. The weak solvent is not particularly limited, and may be water, methane, butyl cellosolve, acetone or toluene. C3 _ [Molecular weight] From the viewpoint of controlling the molecular weight, the diacid derivative (tetracarboxylic dianhydride, acid chloride and dialkyl ester) is preferably used in the polymerization, and the molar ratio is 1:0.7 to 1:1.2. The molecular weight of the obtained polyimide precursor will increase. The molecular weight of the precursor will affect the viscosity of the resin, and the polyimine film will cause uniformity of the resin coating when the molecular weight of the polyimide precursor is too large. The molecular weight is too small, and the obtained polypyrene is insufficient. Therefore, the molecular weight of the polyamidiamine precursor composition of the present invention is preferably a molecular weight of 500,000, preferably 5,000 to 300,000, more preferably 100.000. d. [Production of Polyimine] The polyimine of the present invention can be obtained by imidating the above polybenzazole. The polyethylenimine precursor is produced from the polyamidiene precursor and added from the diamine component and the fourth The pre-liquid obtained by the reaction of the carboxylic acid dianhydride can be easily subjected to chemical ruthenium iodization. The temperature of the chemical hydrazine is subjected to hydrazine imidization reaction, and the molecular weight of the ruthenium iodide is preferred. Ester powder. Ratio of alcohol, ethanol, hexylamine component to tetracarboxylic dicarboxylic acid) The ear ratio is approximately 1: the physical strength of the polyimide, the coating workability and the strength of the amine film will be 2,000 Å to 10,000 Å to the imine precursor amide, the catalyst will be described. Polyammonium acid amination can not be lowered in the lower stage. Poly-63- 201033249 Chemical hydrazine imidation can be carried out by stirring the imidized imidized polymer in the presence of a basic catalyst and an acid anhydride in an organic solvent. get on. As the organic solvent, the solvent used in the above polymerization reaction can be used. Basic catalysts such as pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferred because it has a moderate alkalinity in carrying out the reaction. Further, an acid anhydride such as acetic anhydride, trimellitic anhydride, pyromellitic anhydride or the like is preferable, and in the case of using acetic anhydride, it is preferred to carry out the reaction after completion of the reaction. The temperature at which the oxime imidization reaction is carried out is -20 ° C to 140 ° C, preferably _ 〇 ° C to 100 ° C, and the reaction time may be from 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amino acid group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles of the amidate group. Ear times. The ruthenium imidation ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time. The solution after the imidization reaction may remain in the added catalyst or the like. Therefore, it is preferred to recover the obtained quinone imidized polymer by the following method, and then re-dissolve as an organic liquid solvent as the liquid crystal alignment agent of the present invention. use. The polymer obtained by precipitating the polyimine solution obtained above while injecting a weakly soluble Q agent can precipitate the polymer. After several times of precipitation, it is washed with a weak solvent, and then dried at room temperature or by heating to obtain a purified polyphthalate powder. The weak solvent is not particularly limited, and may be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or the like. e. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent-forming coating liquid obtained by uniformly dissolving the above-mentioned polyimine precursor-64-201033249 or polyimine in an organic solvent. . El·[Solvent] The solvent used in the liquid crystal alignment agent of the present invention is, for example, a solvent capable of dissolving a polyimine precursor or a polyimide, (hereinafter referred to as a good solvent), and an application of the liquid crystal alignment agent to the liquid crystal alignment agent There are two kinds of solvents (hereinafter referred to as weak solvents) for uniformity of coating film at the time of substrate. The good solvent may be one which is capable of dissolving a polyimine precursor or a polyimine, and is not particularly limited. Specifically, for example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl -2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, dimethyl hydrazine, hexamethylarylene, γ-butyl Lactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-indole, hydrazine-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even if it is used alone, the solvent of the ruthenium polymer is not dissolved, and it may be used in combination within the range in which the polymer is not precipitated. The weak solvent may be one which can improve the uniformity of the coating film with a low surface tension, and is not particularly limited. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol-acetate, propylene glycol diacetate, propylene glycol-1-single Methyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactate η -propyl ester, η-butyl lactate, isoamyl lactate, and the like. These solvents -65- 201033249 can be used in two or more types. [Chane coupling agent] The sand compound coupling agent is an organic hydrazine compound having both an organic functional group capable of chemically bonding an organic material in a molecule and a hydrolyzable group reactive with an inorganic material, and its structure is generally as shown in the following formula (57). Expressed. Q-Rl4-SiR3-nWn (57) In the formula (57), 'Q is an organic functional group, r14 is a divalent organic group 'R is an alkyl group', and W is an alkoxy group represented by ORls ( Wherein r15 is an alkyl group), and η is an integer of from 1 to 3. The purpose of adding a decane coupling agent is to improve the adhesion of various inorganic materials and polymers for the substrate of the electronic device. The decane coupling agent can be hydrolyzed to form a stanol by heating and hydrolyzing alkoxysilane for a water-decomposing group, and then hydrogen bonding or co-bonding with a polar group existing on the surface of the substrate to impart adhesion 〇 is used in the present invention. Specific examples of the decane coupling agent are as follows, but are not limited thereto. 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) -66 - 201033249 Amine-based decane, such as propylamine, 3-aminopropyldiethoxymethyldecane; vinyltrimethoxydecane, vinyltriethoxydecane, ethylene (2-methoxyB) Ethylene such as oxy)decane, vinylmethyldimethoxynonenyltriethoxymethoxydecane, vinyltriisopropoxydecane, allylmethoxydecane, P-styryltrimethoxydecane Base chelating agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxytriethoxydecane, 3-glycidoxypropylmethyldiethoxyfluorene φ 3 - epoxy decane coupling agent such as glycidoxypropylmethyldimethoxydecane or 2-(3,4-epoxy)ethyltrimethoxydecane; 3-methyloxypropyl A Dimethoxy decane, 3-methacryloxypropyl triyl decane, 3- Propenyl decane such as methacryloxypropylmethyldiethoxydecane, 3-propenyloxypropyltriethoxydecane, etc., such as methacrylyl decane coupling 3-propenyloxypropyltrimethoxydecane Urea-based decane coupling agent such as ureidopropyl triethoxy decane: bis(3-ethoxydecyl)propyl)disulfide, bis(3-(triethoxyindenyl)propyl Sulfide-based decane coupling agent such as tetrasulfide; 3-mercaptomethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-octyl-1-propyltriethoxydecane, etc. a decane coupling agent; an ester-type decane coupling agent such as 3-isocyanopropyltriethoxy decane or 3-isocyanate propyltrimethoxy decane; or an aldehyde chelating agent such as triethoxy decyl butyl aldehyde; A urethane-based chelating agent such as triethoxysulfonylpropylmethylaminoformate or (3-trimethyldecylpropyl)-t-butylcarbamate. The decane coupling agent can be bonded to the polymer base 3 in the organic functional group Q, ethyl ethene propyl group, cyclohexyl propylene methoxymethyl agent; 3-(trioxanepropyl sulfonate) The cyanoalkyl acetosiloxane oxime functional group -67-201033249 is introduced into the polymer to further exert its effect. Therefore, the decane coupling agent is preferably used in the composition of the polyimine precursor or polyimine used. When the polyimide film is used in an electronic device such as a liquid crystal display device, it is preferable to introduce a decane coupling agent at the end of the polymer in order to improve the adhesion, and the polyimide and the quinone imine. The polyimine of the polymer can adjust the molar ratio of the tetracarboxylic acid derivative such as tetracarboxylic dianhydride, acid chloride and dialkyl ester dicarboxylic acid to the diamine compound to make the polymer terminal functional The base is an amine, a carboxylic acid or an ester. Therefore, an epoxy decane coupling agent having a higher reactivity with respect to such a functional group, an isocyanate decane coupling agent, an aldehyde decane coupling agent, an urethane decane coupling Mixture, amine decane coupling agent Preferably, the amine decane coupling agent and the epoxy decane coupling agent are particularly preferred from the viewpoint of reactivity. Further, by modifying the polymer terminal by a known functional compound, any functional group can be introduced into the polymer. It is preferred to add a decane coupling agent having an organic functional group Q reactive with the introduced functional group. When the coupling agent is added, the coupling agent may be added to react with the polymer by heating to enhance the adhesion. Thereafter, the reaction can be carried out at 20 to 80 ° C, preferably at 40 to 60 ° C for 1 to 24 hours. e3. [Other Additives] The liquid crystal alignment agent of the present invention may additionally use various additives such as a crosslinking agent. The polymer contained in the imine precursor or the polyimide composition may be two or more kinds. -68- 201033249 e4. [Polymer concentration] The polymer concentration of the liquid crystal alignment agent of the present invention can be set as desired. The film thickness of the polyimide film is appropriately changed, but is preferably from 1 to 10% by mass, and more preferably from 2 to 8% by mass. When it is less than 1% by mass, it is difficult to form a uniform and defect-free coating film, more than 10 When the mass is %, the preservation stability of the solution is deteriorated. f. Method for producing crystal alignment agent] The liquid crystal alignment agent of the present invention can be produced by the following method. When the polymer used is a powder, it is dissolved in the solvent to form a polymer solution. At this time, the polymer concentration is preferably 10 to 30 mass. %, particularly preferably from 10 to 15% by mass. It can be heated when the polymer powder is dissolved. The heating temperature is preferably from 20 to 140 ° C, particularly preferably from 20 to 80 ° C. The solvent and the aforementioned uniformity of the coating film are uniform. The liquid crystal alignment agent of the present invention can be obtained by adding a solvent solution of the polymerization Φ or a polymer solution obtained by redissolving the polymer to a certain polymer concentration. The precipitation of the decane coupling agent is prevented in order to prevent precipitation. The polymer is preferably added before the addition of the solvent for improving the uniformity of the coating film. When the amount of the decane coupling agent added is too large, the unreacted substance has an adverse effect on the liquid crystal alignment property, and when it is too small, the adhesion is not effective, so it is preferably from 0.01 to 5.0% by mass based on the polymer powder.佳. ο.! to 1.0% by mass - 69 - 201033249 g. [Liquid Crystal Alignment Film] The liquid crystal alignment film of the present invention can be obtained from the following. That is, the liquid crystal alignment agent of the present invention is preferably applied to a substrate after filtration, dried, and calcined to form a coating film. The substrate for coating the liquid crystal alignment agent of the present invention is not particularly limited, and a substrate having a high transparency can be used, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used, and the steps are simplified. It is preferable to use a substrate which forms an ITO electrode for driving a liquid crystal. Further, when only a single-sided substrate is used for the reflective liquid crystal display device, an opaque material such as a circuit board can be used. In this case, a material capable of reflecting light such as aluminum can be used as the electrode, and a coating method of the liquid crystal alignment agent of the present invention can be used. , spin coating method, printing method, inkjet method, and the like. After the liquid crystal alignment agent of the present invention is applied, it is preferably dried and calcined. In order to sufficiently remove the organic solvent contained in the liquid crystal alignment agent, it is preferably dried at 50 to 120 ° C for 1 to 1 minute. Next, it is preferably calcined at 150 to 3 ° C, more preferably 150 to 250 ° C. The calcination time varies depending on the calcination temperature, but is preferably 5 to 120 minutes, more preferably 5 to 60 minutes. The liquid crystal alignment agent of the present invention will be as described above by the above-mentioned coating film. The Boc-protected primary or secondary aliphatic amine group possessed by the polyamidene precursor or its quinone imidized polymer at a temperature above 150 ° C, desorbs from the Boc group to form a detachment protected by a Boc group. Reactive grade 1 or 2 aliphatic amine groups. The resulting primary or secondary aliphatic amine group reacts with a functional group present in the polyimine precursor or its oxime imidized polymer to form intermolecular crosslinks, and via the crosslinking reaction, Invention-70-201033249 The obtained liquid crystal alignment film can obtain a polyimide film which does not cause film peeling or scratching when the mechanical strength is increased and friction is applied. The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but when it is too thin, the reliability of the liquid crystal display element is lowered, so it is required to be 5 to 300 nm, preferably 10 to 200 nm. It can be used as a liquid crystal alignment film by rubbing the alignment treatment of the coating film surface or the like. The method of treating the liquid crystal alignment film of the present invention is, for example, a rubbing method, an optical φ alignment treatment method, or the like. Specifically, for example, a method of imparting a polarized radiation to a surface of the coating film in a predetermined direction and then heat-treating at 150 to 250 ° C to impart a liquid crystal alignment energy. Radiation can be used with ultraviolet light having a wavelength of 100 to 800 nm and visible light. Among them, ultraviolet rays having a wavelength of 100 to 4 Å Onm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment, the coated substrate can be heated at 50 to 250 ° C and the radiation can be irradiated. The irradiation amount of the aforementioned radiation is preferably from 1 to 10,000 mj/cm2, particularly preferably from 100 to 5,000 mJ/cm2. [Embodiment] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. [Examples] The following are the codes and structures of the compounds used in the examples and comparative examples. -71 - 201033249 CBDA : Cyclobutane tetracarboxylic dianhydride 1,3 DMCBDE-C1: dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-di Carboxylic acid ester p_PDA : p-phenylenediamine DA-A: diamine DA-B of the above formula (A): diamine DA-D of the above formula (B): diamine DA- of the above formula (D) E ··Diamine DA-F of the above formula (E): diamine DA-H of the above formula (F): diamine of the above formula (H) [Chem. 83]

(Organic solvent) NMP: N-methyl-2-pyrrolidone BCS : butyl cellosolve DMF : Ν, Ν-diethylformamide THF: tetrahydrofuran γ-BL : γ-butyrolactone 1H-NMR, viscosity , determination of molecular weight and friction resistance 201033249 method. &quot;H-NMR] Apparatus: Leaf Fourier-type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (Varian) 400MHz Solvent: Dihydrogenated dimethyl sulfoxide (DMSO-d6) or heavy hydrogen chloroform (CDClj) φ Reference material: Tetramethyl decane (TMS) [Viscosity] The viscosity of the polyamidomate and the polyaminic acid solution in the synthesis example is the E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.). The sample amount was 1.1 mL, the cone rotating portion TE-1 (1°34', R24), and the temperature was 25 °C. [Molecular weight] φ Further, the molecular weight of the polyglycolate is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Μη) calculated from polyethylene glycol or polyethylene oxide. And the weight average molecular weight (hereinafter also referred to as Mw) is calculated. GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Column: manufactured by Shodex (KD803, KD805, IJ)

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (LiBr · H20 for the additive is 30 mmol / L 'phosphoric anhydride crystals (0-phosphoric acid) -73- 201033249 30mmol/L, tetrahydrofuran (THF) is l〇ml/L) Flow rate: 1.0ml/min. Quantitative line preparation standard sample: TSK standard polyethylene oxide made by Tosoh Corporation (weight average molecular weight (Mw) about 900,000 '150,000, 100.000' 30,000), and polyethylene glycol (maximum molecular weight (Mp) of about 12,000, 4,000, 1, 〇〇〇) manufactured by Poliman. In order to avoid peak overlap, two samples of 900,000, 1 〇〇, 〇〇〇, 12,000, and 1.000 were mixed and 2 samples of 150,000, 30,000, and 4,000 samples were mixed. [Tear resistance of polyimine film] The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then baked at 23 ° C for 20 minutes or 60. In a minute, a polyimide film having a film thickness of 100 nm was formed. After rubbing the polyimide film, the surface state of the polyimide film was observed to evaluate the presence or absence of friction scars, the presence or absence of the polyimide film, and the presence or absence of the polyimide film peeling [voltage holding ratio]. The voltage holding ratio of the liquid crystal cell was measured by the following method. A voltage of 4 V was applied between 60 μ8, the voltage after 16.76 ms was measured, and the change from the initial 値 was calculated as the voltage holding ratio. The liquid crystal cell was measured at 23 ° C, 60 ° C, and 9 (temperature of TC) at the time of measurement. -74 - 201033249 [Ion Density] The ion density of the liquid crystal cell was measured by the following method. Using Dongyang Technology Co., Ltd. 6 2 5 4 Measurement by a liquid crystal physical property evaluation device. A triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangular approximation method as an ion density. The liquid crystal cell was measured at 23 ° C and 6 ° C each. Temperature measurement. _ <Example 1> Synthesis of DA-A (synthetic precursor 1) [Chem. 84]

〇2N

1) bh3-thf 2) aq. HCl

3) aq. NaOH 2 -Cyano-4-nitroaniline (I5g, 92mmol) was added to a 1L four-necked flask with a dimro condenser and a l〇〇mL dropping funnel. 400 mL of THF was added and cooled to 〇 °c. Next, a borane-THF complex (1 M in THF, 100 mL '100 mmol) was added dropwise from the dropping funnel over 30 minutes. After confirming that gas was generated in the reaction system, a yellow solid precipitated. After the completion of the dripping, the mixture was stirred at room temperature for 2 days. After completion of the reaction, an aqueous hydrochloric acid solution (2N, 200 mL) was added, and the mixture was stirred at room temperature for 2 hours, and then aqueous sodium hydroxide solution (2N '250 mL) was added at 10 ° C to afford basics and then extracted with dichloromethane. After washing with saturated brine (500 mL), the mixture was dried over magnesium sulfate, and then evaporated and evaporated. The yield was -75-201033249 1 1. 9 g, and the yield was 7 7 %. (Synthetic precursor 2) [Chem. 85]

V〇^CH3 〇2N h3c ch3

The aforementioned cyano reduction product (4.60 g, 27.5 mmol) and dichloromethane (900 mL) were added to a 1 L eggplant type flask, and then di-tert-butyl dicarbonate (Boc 2 oxime) (6.00 g, 27-5 mmol) was added. The solution was stirred at room temperature (20 ° C) for 3 days. After completion of the reaction, the reaction solution was washed directly with saturated brine, and the organic layer was separated and dried over magnesium sulfate. After concentrating the organic layer under reduced pressure, the precipitated solid was recrystallized from ethyl acetate-hexane (volume ratio: 2/7) to obtain a B?c adduct of a yellow solid. The yield was 5.25 g and the yield was 71%. (synthetic DA-A) [Chem. 86]

H2N-N Ο h3c ch3 h2 -76- 201033249 Add the aforementioned Boc adduct (5.0g, i8.7mmol) and ethanol (40ml) to a lOOmL eggplant type flask. 'Substituting nitrogen in the system and adding platinum oxide (500mg) Then replace the inside with hydrogen. The reaction mixture in the form of a yellow suspension was stirred at room temperature for 15 hours. After completion of the reaction, ethanol was added to dissolve the precipitated white solid, and the catalyst was removed by filtration through celite. After concentrating the filtrate, the obtained peach solid was recrystallized from ethyl acetate-hexane (volume ratio: 1/2) to give φ pale peach solid. The yield was 3.40 g and the yield was 77%. 1H-NMR of the obtained solid was measured, and it was confirmed to be DA-A. 1 Η-N MR (DMS Ο - d 6, δρρηι) : 1.44(s, 9H) ' 3.87(d, J = 6.3 Hz, 2H), 4.10 to 4.30(m, 4H), 6.27 (dd, J = 2.4 Hz, 8.1 Hz, 1H) ' 6.31 (d, J = 2.4 Hz, 1H)' 6.38 (d, J = 8.1 Hz, 1H), 7.14 (t, J = 6_3 Hz, 1H). &lt;Example 2&gt; Synthesis of DA-B φ (Synthesis of N-Boc-propargylamine) [Chem. 87]

Add propargylamine (25.18 g, 448.448 mol), triethylamine (55.52 g, 0.549 mol) and 400 ml of dichloromethane to a four-necked flask, while cooling the reaction solution in a water bath (20 ° C), at 30 Dicarbodi-tert-butyl ester (118.15 g, 541.541 mol) was added dropwise in minutes. After the completion of the dropwise addition, the mixture was stirred for 2 hours -77 to 201033249, and then 300 ml of a saturated saline solution and 200 ml of dichloromethane were added to the reaction solution for extraction. The obtained organic layer was dried over magnesium sulfate, and then the solvent was removed, and the solvent of the obtained solution was evaporated to give a pale yellow oil. After recrystallization (hexane), white solid N-Boc-propynylamine (yield: 47.01 g, yield: 6 7.6%) was obtained. (synthetic nitro compound)

2 -Phen-4-nitrobenzamine (5.11 g, 19.4 mmol), bis(diphenylscale)palladium(II)-chloride (281.7 g, 0.401 mmol), copper albinate (160.7 mg '0.8 44 mmol) 30 ml of diethylamine was placed in a four-necked flask after nitrogen substitution, and stirred at room temperature (20 ° C) for 10 minutes. Thereafter, N-Boc-propargylamine (3.72 g, 24.0 mmol) was added, and the mixture was stirred at room temperature (20 ° C) for 4 hours. After confirming the disappearance of the starting material by HPLC (High performance liquid chromatography), 200 ml of ethyl acetate and 200 ml of a 1 mL aqueous ammonium chloride solution were added thereto for extraction. The obtained organic layer was washed twice with a 1 mL aqueous solution of ammonium chloride and dried over magnesium sulfate. The desiccant was removed, and the filtrate was concentrated and purified by silica gel column chromatography (distillate: ethyl acetate:hexane = 3:7 (volume ratio)). The yield was 4.97 g and the yield was -78-201033249 8 8.0%. (synthetic DA-B) [Chem. 89]

NH ❹ The above nitro compound (12.45 g, 42.7 mmol) was placed and suspended in 200 ml of ethanol. The system was degassed by nitrogen (1.23 g), replaced with hydrogen, and stirred at room temperature (20 ° C). The mixture was filtered through celite, and the solvent was removed by removing palladium carbon. After 100 ml of toluene was added, a solid obtained by recrystallization of 50 ml of hexane was added to give a pale brown solid (yield: 9.13 g, I. 1H-NMR of the obtained solid was determined to be DA-B. 1 H-NMR (DMSO- D6,δρριη) : 1 . 3 8 (s, J = 7.2Hz, 2H) ' 2.30(t, J = 7.2Hz, 2H), 2.94( 2H), 3.88 ~4·22(χη, 4H), 6.22( Dd, J = 2. 1 Hz; 6.25 (d, J = 2.1 Hz, 1H) ' 6.37 (d, J = 8.1 Hz, J = 6.0H z, 1H) o

&lt;Example 3&gt; After synthesizing DA-D into a four-necked flask, palladium on carbon P was added for 2 days. The solid obtained thereafter is dissolved. Drying under reduced pressure! Rate: 8 0 · 6 % ) 9H), 1.57 (q, juin, J = 6.0 Ηz, 8.1 Hz, 1H) &gt; 1H), 6.84 (t, -79- 201033249 (synthetic nitro ) [化90]

Boc-glycine (10 g, 58.05 mm) was placed in a nitrogen-substituted four-necked flask and dissolved in THF 150 ml. After adding N-methylmorpholine (NMM) (11.93 g, 117.9 mmol), it was cooled to -20 °C. Isobutylchloroformate (9.99g » 73.14mmol) is added dropwise to the solution. At this time, be careful not to let the temperature of the reaction solution be 〇. (: Above. After stirring, -20 ° C, stirring for 0 minutes. At this time, the reaction solution will be cloudy. After 10 minutes, 2-amino-4-nitroaniline (8.86 g, 57.86 mmol) was added dropwise using a dropping funnel. 360 ml of THF solution. After the completion of the dropwise addition, @ stirring for 1 hour at -20 ° C, followed by stirring at room temperature (20 ° C) for 18 hours. After 18 hours, the precipitated solid was filtered off, and the obtained filtrate was distilled off. The solvent was obtained to obtain a concentrated solution. 200 ml of ethyl acetate and 200 ml of a 1 M aqueous potassium dihydrogen phosphate solution were added to the concentrated solution for extraction. The obtained organic layer was washed once with 1 M potassium dihydrogen phosphate aqueous solution, and then washed with saturated brine. Then, it was washed twice with a saturated aqueous solution of sodium hydrogencarbonate, and then washed once with saturated brine. The organic layer was dried over magnesium sulfate, and then the solvent was removed, and the solvent was evaporated from the solvent to give an orange solid. The solid was suspended in 300 ml of toluene, and the mixture was heated and scrambled for 30-80 to 201033249 minutes. After the solid was collected by suction, the obtained solid was subjected to iH-NMR to obtain the desired nitro compound (yield: 9-85 g, yield: 54.9%). (synthetic DA-D) [Chem. 91]

After adding the aforementioned nitro compound (9.85 g, 31.75 mmol) to the eggplant type flask, 150 ml of ethanol was added. After replacing the reaction vessel with nitrogen, palladium (1·1 1 g, 10% by weight based on the mass of the nitro compound) was added, followed by substitution with nitrogen. Next, the reaction vessel was replaced with hydrogen and stirred at 20 ° C for 48 hours. After the end of the reverse φ, the mixture was filtered through diatomaceous earth to remove palladium carbon, and the solvent was distilled off from the filtrate. 50 ml of toluene was added to the obtained concentrate, and heated to reflux to precipitate a solid. The precipitated solid was filtered while hot to give a lavender solid. The yield was 8.05 g and the yield was 90.4%. 1H-NMR of the obtained solid was measured, and it was confirmed to be DA-C. • H-NMRiDMSO-de, δρριη): 1.40(s, 9H) ' 3.70(d, J = 6.0Hz, 2H), 4.04(bs, 2H), 4.35(bs, 2H), 6.23 (dd, J = 2.4 Hz, 8.0Hz, 1H) &gt; 6.48(d, J = 8.0Hz, 1 H), 6.6 1 (d, J = 2.4Hz, 1H), 7.05(t, J = 6.0Hz, 1H), 8_94(s , 1H). -81 - 201033249 &lt;Example 4&gt; Synthesis of DA-E (synthetic nitro compound)

2-Amino-4-nitroaniline (4.36 g, 28.47 mmol), Ν-α, im--t-butoxy pseudo-L-histidine (14_6 lg, 33.70 mmol) and 4-N N-dimethylaminopyridine (4-DMAP) (1.78 g, M 57 mm 〇1) was placed in a four-necked flask, and DMF 15 〇 ml was added. After nitrogen substitution, 丨_ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDAP) (6.5 8g '34.32mmol) was added and stirred at 20 ° C for 18 hours. . After the completion of the reaction, ethyl acetate and pure water were added to the reaction solution for extraction. The obtained organic layer was washed twice with pure water and dried over magnesium sulfate. After removing the desiccant, the filtrate was concentrated to give an oily compound. 150 ml of toluene was added to the oily compound, and the mixture was stirred under heating to precipitate a yellow solid. The resulting yellow solid was filtered off and dried under reduced pressure. The iH-NMR was measured, and the obtained yellow solid was identified as the objective diamine compound DA-3. Yield: 5.74 g, yield: 41.1%. (synthetic DA-E) -82- 201033249 [Chem. 93]

The above nitro compound (5.74 g, 11.70 mmol) was placed in an eggplant flask, and then 150 ml of ethyl acetate was added. After replacing the reaction vessel with nitrogen, palladium carbon (® 59.59g) was added and replaced with nitrogen. Next, the reaction vessel was replaced with hydrogen and stirred at 20 ° C for 48 hours. After the completion of the reaction, the mixture was filtered through celite, and palladium carbon was removed, and the solvent was evaporated from the filtrate. The product was oily, but after adding 10 ml of toluene, a lavender solid was precipitated by ultrasonic waves. The precipitated solid was heated and dissolved, and then cooled in a water bath to be recrystallized. The precipitated solid was suction-filtered, and then dried under reduced pressure to give a pale solid. Yield · · 2.3 6g, yield: 43.8%. 1H-NMR of the obtained solid was measured, and it was confirmed to be DA-D. 'H-NMRC DMSO-de, 6 ppm): 1.36 (s, 9H)' 1.56 (s, 9H) Lu, 2.76~2.96 (m, 3H), 4.04 (bs, 2H), 4.35 (bs, 2H), 6.25 ( Dd, J = 2.4 Hz, 8.4 Hz, 1H), 6.48 (d, J = 8.4 Hz, 1H), 6.55 (d, J = 2.4 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 7.29 (s, 1H), 8. 1 3 (s, 1H), 9.1 1 (s, 1H). &lt;Example 5&gt; Preparation of a solution of polyglycolic acid (Al) P-PDA 1.125 g (10.40 mmol), DA-B 0.689 g (2.696 mmol), and NMP 30.62 g were placed in a stirring device and a nitrogen introduction tube. In a 30 OmL four-necked flask, nitrogen was added while stirring and dissolved. While stirring the diamine-83-201033249 solution, 2.424 g (12.36 mmol) of CBDA was added, and NMP was added thereto to have a solid concentration of 10% by mass, and stirred at room temperature for 24 hours to obtain poly-proline (A-1). Solution. The viscosity of the polyaminic acid solution at a temperature of 25 ° C was 138.6 mPa · s. The molecular weight of the polyproline is

Mn = 1, 6,079, Mw = 33.544. &lt;Example 6&gt; Preparation of a solution of poly-proline (A-2) p-PDA 1.03 7 g (9.58 9 mmol), DA-D 0.67 1 g (2394 mmol), and NMP 28.3 7 g were placed in a stirring apparatus and The nitrogen inlet tube was placed in a 300 mL four-necked flask, and nitrogen was added while stirring. While stirring the diamine solution, 2.277 g (1 1.61 mmol) of CBDA was added, and NMP was added thereto to have a solid concentration of 10% by mass, and stirred at room temperature for 24 hours to obtain polyglycine (A-2). Solution. The viscosity of the polyaminic acid solution at a temperature of 25 ° C was 146.2 mPa · s. Further, the molecular weight of the poly-proline is Mn = 17,260, Mw = 34, 5 3 2 ° &lt;Example 7&gt; The solution of the poly-proline (A-3) is prepared. p-PDA 0.951 g ( 8.794 mmol) DA-E 1.012g (2.997mm〇l) and NMP 29.10g were placed in a 300 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and stirred and dissolved while feeding nitrogen. While the diamine solution was stirred, 2.095 g (10.69 mmol) of CBDA was added. Further, NMP was added to adjust the solid content to mass%, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (A-3). The polyglycine solution had a viscosity of 157.3 mP a·s at a temperature of 25 t. Further, the molecular weight of the poly-proline is -84 - 201033249 is Mn = 20,610, Mw = 40,640 ° &lt;Comparative Synthesis Example 1&gt; Preparation of a solution of poly-proline (Bl) p-PDA 1.621 g (14.99 mmol) and NMP 28.96 g was placed in a 300 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and stirred and dissolved while feeding nitrogen. While stirring the diamine solution, CBDA 2^7g (14.74mmol) was added, and NMP was added thereto to have a solid concentration of 1% by mass φ, and then stirred at room temperature for 24 hours to obtain polylysine (B-1). Solution. The temperature of the polyaminic acid solution is 25. (The viscosity underneath is 152.7 mPa·s. The molecular weight of the polyamic acid is Mn = 13,972, Mw = 30,181. &lt;Example 8&gt; Modulation of liquid crystal alignment agent (A-1)

After dissolving 12.59 g of the polyplycosic acid (A-1) solution obtained in Example 5 in a 50 mL Erlenmeyer flask placed in a stir bar, 4.11 g of NMP and 4.19 g of BCS were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal. Orienting agent (A - 1). &lt;Example 9&gt; Preparation of liquid crystal alignment agent (A-2) After dissolving 11.37 g of a solution of polyglycine (A-2) obtained in Example 6 in a 50 mL Erlenmeyer flask placed in a stir bar, NMP 3.80 g was added. And BCS 3_79g' was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (A-2). &lt;Example 10&gt; Modulation of liquid crystal alignment agent (A-3) -85-201033249 After the lysine solution (A-3) obtained in Example 7 was dispensed in a 50 mL Erlenmeyer flask in which a stir bar was placed, ll 17 g was added, and then NMP was added. 3.74 g and BCS 3.76 g were stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (A-3). &lt;Comparative Example 1&gt; Preparation of Liquid Crystal Aligning Agent (B-1) After dissolving 12.98 g of the polylysine (B-1) solution obtained in Comparative Synthesis Example 1 in a 50 mL Erlenmeyer flask placed in a stirrer, NMP 4.42 g was added. And BCS 4.2 7g, after stirring for 30 minutes using a magnetic stirrer, the liquid crystal alignment agent (B-1) was obtained. &lt;Example 1 1&gt; The liquid crystal alignment agent (Α-1) obtained in Example 8 was filtered using a filter of 1.0 μm, and then spin-coated on a glass substrate with a transparent electrode, and placed on a hot plate of 8 (TC). After drying for 5 minutes and baking at 230 ° C for 20 minutes, a polyimide film having a film thickness of 100 nm was obtained, and the polyimide film was rubbed with a screw cloth (rolling diameter: 120 nm, number of revolutions of 1000 rpm, moving speed of 20 mm/ After sec and the amount of press-in of 醯4 mm), the surface state of the polyimide film was observed, and as a result, no scratches from the rubbing, chipping of the polyimide film, and peeling of the polyimide film were observed. 12&gt; A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal alignment agent (A-2) obtained in Example 9 was used, and rubbing treatment was carried out. The surface state of the polyimide film was observed, and as a result, no observation was observed. From the scratch of the friction, -86-201033249 The chipping of the polyimide film and the peeling of the polyimide film. <Example 13> Example of the liquid crystal alignment agent (A-3) obtained by using Example 1 The method of 11 produces a polyimide film and performs a rubbing treatment. The surface state of the polyimide film, the result No peeling of the polyimide film from the rubbing and the peeling of the polyimide film were observed. ❹ &lt;Comparative Example 2 &gt; Example 11 except the liquid crystal alignment agent (B-1) obtained in Comparative Example 1 was used. The polyimide film was produced and subjected to a rubbing treatment. The surface state of the polyimide film was observed, and as a result, the shaving of the scar imino film from the friction was observed. <Example 14> A filter using Ι.Οιη After filtering the liquid crystal alignment Α-1) obtained in Example 8, it was spin-coated on a glass substrate with a transparent electrode, and then dried on a hot plate for 5 minutes, and baked at 230 ° C for 20 minutes to obtain a polymerization of 100 nm.醯 imine film. After rubbing the polyimide film (120 mm in diameter, 1 rpm, moving speed 20 mm/sec, and 0.4 mm pressure) with a snail cloth, the ultrasonic wave was washed for 1 minute in pure water to remove water. After drying at 80 ° C for 10 minutes, a liquid crystal alignment film was attached. Prepare two substrates with the liquid crystal alignment film, and place the 6μηι distance adjuster on the liquid crystal alignment film surface of one of the substrates, and then twist it by anti-parallel 8 5 , observe the traces, observe and collect the polymer (80 °C). Thickness of the film thickness of the blown substrate -87- 201033249 The conditions of the rubbing direction of the two substrates are combined and sealed around the liquid crystal injection port to form an empty cell of 6 μm. 2003, manufactured by Merck, vacuum injection into the empty cell, and the nematic liquid crystal cell was twisted after sealing the injection port. The alignment state of the liquid crystal cell was observed by a polarizing microscope, and it was confirmed that the liquid crystal cell was uniformly aligned. The voltage of the liquid crystal cell was measured. After the retention rate, the ion density was measured, and the voltage retention was 9 9.3 % at a temperature of 2 3 ° C, 9 8.7 % at a temperature of 60 ° C, 94.1% at a temperature of 90 ° C, and 10 pC at an ion density of 23 ° C. /cm2, 18 pC/cm 2 at 60 ° C &lt;Example 15&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal alignment agent (A-2) obtained in Example 9 was used, and the alignment state of the liquid crystal was confirmed. Measuring electricity The pressure retention ratio and the ion density were observed by a polarizing microscope, and the alignment state of the liquid crystal cell was observed to be a uniform orientation without defects. After the voltage holding ratio of the liquid crystal cell was measured, the density of the ions was measured, and the voltage retention rate was 23°. 99.3% under C, 98.8% at 60 ° C, 94.4% at 90 ° C, and an ion density of 5 pC/cm 2 , 60 at 23 ° C. (: 1 lpC/cm 2 lower. &lt;Example 16&gt; 1) The obtained liquid crystal alignment agent (A-3) was prepared in the same manner as in Example 14 to prepare a twisted nematic liquid crystal cell, and the alignment state of the liquid crystal, the measured voltage holding ratio, and the ion density were confirmed. The liquid crystal at normal temperature (MLC-88- 201033249 2003, manufactured by Merck Co., Ltd.) vacuum-injected into the empty cell, and sealed the injection port to twist the nematic liquid crystal cell. The alignment state of the liquid crystal cell was observed by a polarizing microscope, and it was confirmed to be a uniform alignment without defects. The voltage of the liquid crystal cell was measured. After the retention rate, the ion density was measured, and the voltage retention was 9 9.4 % at 23 °C, 9 9 · 1 % at 60 °C, 9 6.7 % at 90 °C, and an ion density of 3 pC at 23 °C. /cm2, 6 0°CT 4pC/cm2. _ &lt; Comparative Example 3 &gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal alignment agent (B-1) obtained in Comparative Example 1 was used, and the alignment state of the liquid crystal, the measurement voltage retention ratio, and the ion density were confirmed. The alignment state of the liquid crystal cell was observed under a microscope, and it was confirmed to be a uniform alignment without defects. After measuring the voltage holding ratio of the liquid crystal cell, the ion density was measured, and the voltage holding ratio was 9 9 · 1 % at 23 ° C, 9 7.4 % at 60 ° C, and 8 6 · 7 % at 90 ° C. The ion density was 50 pC/cm 2 at 23 ° C and 256 pC/cm 2 at 60 ° C. &lt;Example 1 7&gt; Synthesis of DA-F (Synthetic Precursor 1) [Chem. 94]* HBr

Boc20NEi3 CH2C12

3-Bromopropylamine brominated hydrogenation acid (105.10 g, 0.480 mol) was placed in a 2 L four-necked flask, and 978.88 g of dichloromethane and di-tert-butyl dicarbonate (115.13 g ' were added. After 0.528 mol), stir at 0 ° C (ice bath). Next, triethylamine (92.58 g, 0.915 mol) was placed in a dropping funnel, and dropped into a slurry solution in a four-necked flask over 30 minutes. After the start of the dropping, the reaction solution was intensely lit, and a white solid precipitated. Stir the mixture for 2 hours after the completion of the drip. After the completion of the reaction, 500 ml of pure water was added to the reaction solution for extraction. The obtained organic layer was washed twice with pure water, and then dried over magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a colorless and transparent oil. 500 ml of hexane was added to the oily substance, and crystallization was carried out at -78 ° C to give a white solid. The solid was collected by suction and dried under reduced pressure. 1H-NMR was measured, and it was confirmed that the obtained white solid was tert-butyl 3-bromopropyl carbamic acid ester. The yield was 89.5 5g and the yield was 7 8 · 3 %. *H NMR (400MHz, CD C13, δ p pm ) : 1.4 4 ( s, 9H ), 2.0 5 ( quin, J = 6.4Hz, 2H), 3.27 (q, J = 6.4Hz, 2H), 3.45(t , J = 6.4 Hz, 2H), 4.69 (bs, 1H). (Synthetic precursor 2) -90- 201033249

1,5-Dihydroxy-4,8-dinitroguanidine (14.04 g, 42.52 mmol) was placed in a four-necked flask, and NMP 3 00 g was added thereto, followed by heating at 80 ° C to obtain 1,5-dihydroxy- The 4,8-dinitroguanidine is completely dissolved. Potassium carbonate (12. Olg, 86.9 5 mmol) and potassium iodide (2 8.77 g, 1 73.33 mmol) were added to the above solution, and then tert-butyl 3-bromopropyl carbazate (30.40 g, 127.7 mm 〇l) was added. Then, the mixture was heated and stirred at 80 ° C for 6 hours. The obtained reaction solution was poured into 500 ml of a 〇·5Μ aqueous hydrochloric acid solution, and then ethyl acetate (500 ml) was added thereto for extraction. The obtained organic layer was washed with a 0.5 M aqueous hydrochloric acid solution and brine, and dried over magnesium sulfate. After removing the desiccant, the solvent was distilled off, and the residue was purified by silica gel chromatography (distillate: 1,2-dichloroethane:ethyl acetate = 7:3 (volume ratio)) to obtain a yellow solid. The NMR was measured, and it was confirmed that the obtained yellow solid was the above-mentioned nitro compound. The yield was 3.21 g and the yield was 11.7%. *H NMR(400MHz, CDC13, δρρηι) : 1.42(s, 18Η), 2.13( quin, J = 6.0Hz, 4H), 3.4 1 (q, J = 6.0 H z, 4 H ), 4.2 8 9 (t , J = -91 - 201033249 6.0Hz, 4H), 5.28(bs, 2H), 7.23(d, J = 8.8Hz, 2H), 7.93(d, J = 8.8Hz, 2H). (synthetic DA-F) [Chem. 96]

The above dinitro compound (1.48 g, 2.30 mmol) and sodium sulfide nonahydrate (5-72 g, 23-82 mmol) were placed in a four-necked flask, and 5 ml of pure water was added thereto, followed by heating under reflux for 2 hours. After the reaction solution was cooled to room temperature, a 2 mass% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred at 50 ° C for 1 hour. After suctioning the solid in the reaction solution, it was washed with pure water. The obtained solid was recrystallized and purified to give a purple solid. The obtained purple solid was confirmed to be a diamine (F) by 1H-NMR. The yield was 〇15 g and the yield was 11.2%. !H NMR (400MHz, CDC13, 6ppm): 1.49(s, 18H), 2.06( quin, J = 5.6Hz, 4H), 3.48(q, J = 5.6Hz, 4H), 4.12(t, J = 5.6Hz , 4H), 6.54 (bs, 42H), 6.92 (d, J = 9.2 Hz, 2H), 7.06 (m, 201033249 2H), 7. 1 6 (d, J = 9.2 Hz, 2H) 0 &lt;Examples 18&gt;Synthesis DA-H (Synthetic Precursor 1)

[化97]

2,6-Diiodo-4-nitroaniline (50.008, 128111111〇1), bis(triphenylphosphine)palladium(II) dichloride (900 mg, 1.2 8 mmol), confirmed copper (488 mg, 2.56 mmol) ), diethylamine 32 ml and THF 165 ml were added to a 1 L four-necked flask, and stirred at room temperature (20 ° C) for 10 minutes. After stirring the solution in the four-necked flask, N-Boc-propyl was added dropwise over 15 minutes. An alkyneamine (47.60 g, 307 mmol) in THF (90 mL). After the completion of the dropping, the mixture was stirred at room temperature (20 ° C) for 12 hours. After 12 hours, the reaction solution was poured into 1.28 L of pure water which was stirred, and the precipitated black precipitate was suction-filtered and washed twice with 50 ml of water. The obtained solid was dried under reduced pressure to give a brown solid. The brown solid was recrystallized (toluene) and purified to give a yellow solid. The yellow solid obtained by the measurement of 'H-NMR was confirmed to be the above-mentioned nitro compound. The yield of 201033249 was 47.09 g, and the yield was 83.0%. !H NMR (400MHz, CDC13, 6ppm): 1.48 (s, 18H), 4.16 (d, J = 6.0Hz, 4H), 4.93 (bs, 2H), 5.78 (bs, 2H), 8.09 (s, 2H) . (synthetic DA-H) [Chem. 98]

The above nitro compound (47.07 g, 106 mmol) was placed in a 1 L four-necked flask and suspended in 560 ml of ethanol. After the system was degassed and replaced with nitrogen, palladium carbon (4.71 g) was added and then replaced with hydrogen. After heating and stirring at room temperature (50 ° C) for 8 days, palladium carbon was removed by filtration using diatomaceous earth, and the solvent was distilled off. The obtained solid was dissolved in 200 ml of 1,2-dichloroethane, and then 70 ml of hexane was added thereto to carry out recrystallization. The obtained solid was dried under reduced pressure to give a white solid. The yield was 39.54 g and the yield was 87.5%. The obtained solid was subjected to A-NMR, and was confirmed to be DA-H. 'H NMR (400MHz, CDC13, 5ppm): 1.45(s, 18H), 1.78( quin, J = 6.4Hz, 4H), 2.48(t, J = 6.4Hz, 4H), 3.45(q, J = -94 - 201033249 6·4Ηζ, 4H), 4.69(bs, 1H), 6.36(s, 1H). &lt;Example 19&gt; Preparation of a solution of poly-proline (A-4) p-PDA 1.728 1 g (1 6.47 mmol), DA-A 0.9 5 0 9 g (4.07 mmol) and NMP 46.12 g were attached The sample evacuation device and the nitrogen introduction tube were placed in a 100 mL four-necked flask, and nitrogen was added while stirring. While stirring the diamine solution, CBDA 3.8093 g (19.43 mmol) was added, and then 0 NMP was added thereto to have a solid concentration of 1 〇 mass%, and the solution of polyglycine (A-4) was stirred at room temperature for 24 hours. The polyglycine solution had a viscosity at 25 ° C of 149 mPa·s. Further, the molecular weight of the poly-proline was Mn = 18,136, Mw = 37,265 〇 &lt;Example 20&gt; The solution of the poly-proline (A-5) was adjusted to p-PDA 0.8665 g ( 8.01 3 mmol ) , DA- H 0.8442g (1.998 mmol) and NMP 25.31 g were placed in a φ 1 OO mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and stirred and dissolved while feeding nitrogen. While stirring the diamine solution, CBDA 1.9047 g (9.713 mmol) was added, and NMP was added thereto to have a solid concentration of 10% by mass. After stirring at room temperature for 24 hours, a solution of polyamine acid (A-5) was obtained. The viscosity of the polyaminic acid solution at a temperature of 25 ° C was 254.7 mPa · s. Further, the molecular weight of the poly-proline is Mn = 27,447, Mw = 59,03. &lt;Example 21&gt; Modulation of polyphthalate resin (C-1) p-PDA 2.00 g (18.5 mmol) under nitrogen, DA-D 1.2269 g -95- 201033249

(4.624mmol), NMP 167.67g and the test 0. 4.2 1 g (53_26mmol) was placed in a 300mL four-necked flask equipped with a stirring device and stirred to dissolve. Next, while stirring the diamine solution, 7.216 g (22.19 mmol) of 1,3DM-CBDE-C1 was added, and the reaction was carried out for 4 hours under water cooling. The obtained solution of the polyphthalate was put into 882 g of water which was stirred, and the precipitated white precipitate was collected by filtration. Then, the mixture was washed once with water (8,89 g), and then washed with ethanol (8,82 g), and then washed three times with 221 g of ethanol, and dried to obtain 7.22 g of a white polyphthalic acid ester resin powder (C-1). The yield was 81.8%. Further, the molecular weight of the polyamidite ester was Mn = 20,469 and Mw = 40,025. &lt;Example 22&gt; Modulation of polyphthalate resin (C-2) P-PDA 2.00 g (1 8.50 mmol) of 'DA-B 1.296 1 g (4.624 mmol), NMP 1 6 8.9 8 g under nitrogen The pyridine 4·2 1 g (53.26 mm 〇l) for the base was placed in a 300 mL four-necked flask equipped with a stirring device, and stirred to dissolve. Next, while stirring the diamine solution, 7.216 g (22.19 mmol) of 1,3DM-CBDE-C1 was added, and the reaction was carried out for 4 hours under water cooling. The obtained polyphthalate solution was placed in 8 89 g of water which was stirred, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 889 g of water and then washed once with 889 g of ethanol, and then washed three times with 222 g of ethanol, and dried to obtain 7.79 g of a white polyamine resin powder (C-2). The yield was 87.6%. Further, the molecular weight of the polyglycolate was Mn = 20,886' Mw = 45,830. &lt;Example 23&gt; Modification of polyphthalate resin (C-3) P-PDA 1.50 g (13.87 mmol), DA-E 1.5 9 7 g -96-201033249 (3.468 mmol), NMP 65.26 g under nitrogen 3.13 g (3 9.5 3 mmol) of pyridine with a base was placed in a 300 mL four-necked flask equipped with a stirring apparatus, and stirred and dissolved. Next, 1,3DM-CBDE-C1 5.3 5 56g (16.47 mmol) was added while stirring the diamine solution, and the reaction was carried out for 4 hours under water cooling. After 4 hours, NMP 72.5 lg was added to the reaction solution, and the mixture was stirred at room temperature (2 ° C) for 15 minutes. The resulting solution of the polyglycolate was placed in a stirred water of 725 g, and the precipitated white precipitate was filtered off. Subsequently, the mixture was washed once with 725 g of water, and further washed with 725 g of ethanol, and then washed three times with ethanol (81 g), and dried to obtain 3.76 g of a white polyphthalate resin powder (C-3). The yield was 51.8%. Further, the molecular weight of the polyglycolate is Mn = 20,52 5, Mw = 43,3 95. &lt;Example 24&gt; Modification of polyphthalate resin (C-4) 2.50 g (23.11 mmol) of P-PDA, 1.3715 g (5.80 mmol) of DA-A, NMP 9 7.1 6 g and alkali were used under nitrogen. Pyridine 5 · 2 1 g (φ 65.8 9 mmol) was placed in a 300 mL four-necked flask equipped with a stirrer and stirred to dissolve. Next, while stirring the diamine solution, 1,926 g (27.45 mmol) of 1,3DM-CBDE-C1 was added, and the reaction was carried out for 4 hours under water cooling. After 4 hours, 107 g of 95 mg of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 t:) for 15 minutes. The obtained polyphthalate solution was placed in a stirred water of 80 g, and the precipitated white precipitate was collected by filtration. Then, it was washed once with water of 980 g, and then washed once with 1 080 g of ethanol, and then washed three times with 270 g of ethanol, and dried to obtain 9.17 g of a white polyphthalate resin powder (C-4). The yield was 85.2%. The molecular weight of the polyglycolate is Mn = 17,573, -97- 201033249

Mw = 37,258. &lt;Example 25&gt; Modification of polyphthalate resin (C_5) P-PDA 1.4 2 0 g (1 3 · 1 3 mm ο 1 ), DA-H 1.3 872 g (3.283 mmol), NMP 59.54 g under nitrogen The acridine 2_87g (36.24 mmol) for the base was placed in a 300 niL four-necked flask equipped with a stirring device, and stirred to dissolve. Next, the diamine solution was stirred while adding 1,3DM-CBDE-C1 4_9099 g (1 5.1 Ommol) to react under water cooling for 4 hours. After 4 hours, 66.15 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (2 ° C) for 15 minutes. The obtained polyphthalate solution was placed in 662 g of water which was stirred, and the precipitated white precipitate was collected by filtration. Then, it was washed once with 662 g of water and then washed once with 662 g of ethanol. Then, it was washed three times with ethanol i65 g, and dried to obtain 5.11 g of a white polyphthalate resin powder (C-5). The yield was 77.3 %. Further, the molecular weight of the polyamidomate was Mn = 1 4, 72 4, M w = 2 7,1 5 0 〇 &lt;Comparative Synthesis Example 2&gt; Modulation of polyphthalate resin (Dl) Under nitrogen, P- PDA 0.699 g (64.64 mmol), NMP 427.1 g, and base pyridine 11.65 g (1 47.3 8 mmol) were placed in a 50 mL four-necked flask equipped with a stirring apparatus, and stirred to dissolve. Next, the diamine solution was stirred while adding 1,3DM-CBDE-C1 1 9.9657 g (61.41 mmol), and reacted under water cooling for 4 hours. The obtained polyphthalate solution was poured into 2,24 g of water under stirring, and the precipitated white precipitate was filtered off. Then, it was washed once with 2248 g of water, and once with 2248 g of ethanol, and then washed with 562 g of ethanol for 3, 2010,33,249 times, and dried to obtain 22.10 g of a white polyphthalate resin (D-1) powder. The yield was 98.4%. Further, the molecular weight of the polyglycolate was Mn = 16,813, Mw = 3,585 〇 &lt;Example 26&gt; Preparation of liquid crystal alignment agent (A-4) The 50 mL Erlenmeyer flask placed in a stirrer was used to obtain the obtained Example 19. After 6.18 g of a solution of the polyaminic acid (A-4), 1.60 g of NMP and 1.99 g of BCS φ were added, followed by stirring for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A-4) 〇 &lt;Example 27&gt; Liquid crystal alignment agent (A-5) After adding 5.87 g of the polylysine (A-5) solution obtained in Example 20 in a 50 mL Erlenmeyer flask placed in a stir bar, 'NMP 1.15 g and BCS 1.76 g were added, and then The magnetic stirrer was stirred for 30 minutes to obtain a liquid crystal alignment agent (A-5) = &lt;Example 28&gt; The liquid crystal alignment agent (C-1) was prepared. The polyphthalate resin powder obtained in Example 21 was fractionated in a conical flask. After 1.65 g, 14.95 g of γ-BL was added, and the mixture was stirred at room temperature for 24 hours to be dissolved. γ-BL 5.43 g and BCS 5.55 g were added to the solution, and stirred in a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (C-1). &lt;Example 29&gt; Modulation of liquid crystal alignment agent (C-2) The polyphthalate resin powder obtained in Example 22 was fractionated in a conical flask to -99-201033249 at the end of 0.733 g, and γ-BL 6.60 g was added thereto at room temperature. Stir for 24 hours to dissolve. γ-BL 2.48 g and BCS 2.45 g were added to the solution. After stirring for 30 minutes with a magnetic stirrer, a liquid crystal alignment agent (C-2) was obtained. <Example 30> A liquid crystal alignment agent (C-3) was prepared. In a conical flask, 0.907 g of the polyphthalate resin powder obtained in Example 23 was added, and 8.18 g of γ-BL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved. γ-BL 3.06 g and BCS 3.04 g were added to the solution. The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (C-3). &lt;Example 31&gt; Preparation of liquid crystal alignment agent (C-4) 0.802 g of the polyphthalate resin powder obtained in Example 24 was placed in an Erlenmeyer flask, and then 7.23 g of γ-BL was added thereto, and the mixture was stirred at room temperature for 24 hours. It dissolves. γ-BL 2.78 g and BCS 2.68 g were added to the solution, and stirred in a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (C-4). &lt;Example 32&gt; Preparation of liquid crystal alignment agent (C-5) 0.755 g of the polyphthalate resin powder obtained in Example 25 was placed in a conical flask, and then 7.57 g of γ-BL was added thereto, and the mixture was stirred at room temperature for 24 hours. Dissolved. γ-BL 2.65 g and BCS 2.55 g were added to the solution, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (C-5). &lt;Comparative Example 4&gt; Preparation of Liquid Crystal Aligning Agent (D-1) The polyacetate resin obtained in Comparative Synthesis Example 2 was dispensed in a conical flask - 100 - 201033249 powder 2. After 2 g, DMF 9.21 g was added at room temperature. Stir for 24 hours to dissolve. γ-BL 3.29 g and BCS 3.39 g were added to the solution, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (D-1). &lt;Example 33&gt; A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal alignment agent (A-4) obtained in Example 26 was used, and rubbing treatment was carried out. The surface state of the φ polyimine film was observed, and as a result, a scratch from the friction was observed, but it was milder than Comparative Example 2. No peeling of the polyimide film and peeling of the polyimide film were observed. &lt;Example 34&gt; A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal alignment agent (A-5) obtained in Example 27 was used, and rubbing treatment was carried out. The surface state of the polyimide film was observed, and as a result, no scratches from the friction, swarf of the φ polyimine film, and peeling of the polyimide film were observed. &lt;Example 35&gt; The liquid crystal alignment agent (C-1) obtained in Example 28 was filtered using a filter of Ι.Οηηι, and then spin-coated on a glass substrate with a transparent electrode, and then dried on a hot plate at 80 °C. 5 minutes, after 23 hours of TC calcination, a polyimine film having a film thickness of 100 nm was obtained. The polyimine film was rubbed with a screw cloth (roller 120 mm, number of revolutions 1000 rpm, moving speed 20 mm/sec, pressure) After the amount of 〇.4 mm), the surface state of the polyimide film was observed, and as a result, no scratches from -101 - 201033249, scratches on the polyimide film, and peeling of the polyimide film were observed. Example 36&gt; A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal alignment agent (C-2) obtained in Example 29 was used, and rubbing treatment was carried out. The surface state of the polyimide film was observed, and the result was not observed. The scratches from the rubbing, the shavings of the polyimide film, and the polyimide film were peeled off. <Example 3 7> In addition to the liquid crystal alignment agent (C-3) obtained in Example 30, the same was carried out. The method of Example 35 was carried out to prepare a polyimide film for rubbing treatment. The surface of the polyimide film was observed. As a result, the scratches from the rubbing and the shavings of the polyimide film were observed, but it was slightly milder than the comparative example 5 described later. No peeling of the polyimide film was observed. <Example 3 8 &gt; Example 3 1 The liquid crystal alignment agent (C-4) obtained was produced in the same manner as in Example 35, and subjected to a rubbing treatment. The surface state of the polyimide film was observed, and the scratches from the friction were observed. 'But it was slightly milder than Comparative Example 5 described later. No swarf of the polyimide film and peeling of the polyimide film were observed. <Example 39> In addition to the use of the liquid crystal alignment agent obtained in Example 32 ( c -5 ) External 'same-102-201033249 The method of Example 35 was made to produce a polyimide film, and the surface state of the polyimide film was observed. As a result, no shavings and polyimine of the polyimide film were observed. Film peeling. <Comparative Example 5 &gt; In addition to the method of using the liquid crystal alignment obtained in Comparative Example 4, the polyimide film was produced by the method of Example 35, and the surface state of the polyimide film was observed. Film shavings and polyimine film peeling. &lt;Example 40&gt; The liquid crystal alignment obtained in Example 26 was used to prepare a twisted nematic liquid crystal cell, and the voltage holding ratio and the ion density were measured. The alignment state of the crystal unit was confirmed to be the defect-free and the φ crystal unit. The ion density was measured after the voltage holding ratio. The measurement results of the subdensity are shown in Table 1 below. &lt;Example 41&gt; A twisted nematic liquid crystal cell was produced by using the liquid crystal alignment Example 14 obtained in Example 27, and it was confirmed State, and measure voltage retention and ion density. After confirming the voltage holding ratio of the liquid crystal cell without defects after the alignment state of the H liquid crystal cell, the ion-tight left rubbing treatment was measured. Observe the self-friction scar and the agent (D-1), and rub the same. Observe the friction scar, the polymer (Α-4), and the alignment state of the liquid crystal and the liquid crystal. The liquid voltage holding ratio and the separating agent (A - 5 ) were measured, and the alignment of the liquid crystal was observed by the light microscope of the liquid crystal. Determine the ί. Voltage holding ratio and -103-201033249 The measurement results of the ion density are shown in Table 1 below. &lt;Example 42&gt; The liquid crystal alignment agent (C-1) obtained in Example 28 was filtered using a filter of 1. Ομηη, and then spin-coated on a glass substrate with a transparent electrode, and then dried on a hot plate at 80 °C. After baking at 230 ° C for 1 hour for 5 minutes, a polyimide film having a film thickness of 100 nm was obtained. Rubbing the polyimide film with a snail cloth (roller diameter: 120 mm, number of revolutions: 〇〇〇 rpm, moving speed: 20 mm/sec, press-in amount: 0.4 mm), and then washing the pure water for 1 minute for ultrasonic cleaning. After the water droplets were removed by air blowing, they were dried at 80 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with the liquid crystal alignment film were prepared, and a 6 μm shifter was dispersed on the liquid crystal alignment film surface of one of the substrates, and then the rubbing direction of the two substrates was combined under the condition of reverse-parallel twisting of 85 degrees, and the residual liquid crystal was injected. The conditions of the inlet are sealed around, and an empty cell having a cell gap of 6 μm is produced. Liquid crystal (MLC-2003, manufactured by Merck) was vacuum-injected into the empty cell at room temperature, and the nematic liquid crystal cell was twisted after sealing the injection port. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 which will be described later. &lt;Example 43&gt; The twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal alignment agent (C-2) obtained in Example 29 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The orientation state of the liquid crystal cell of -104-201033249 was observed with a polarizing microscope, and it was confirmed that the film was aligned without defects. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 below. <Example 44> A twisted nematic liquid crystal was produced in the same manner as in Example 42 except that the liquid crystal alignment agent (C-3) obtained in Example 30 was used. The unit confirms the alignment state of the liquid crystal, and measures the voltage holding ratio and the ion density. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 which will be described later. &lt;Example 45&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal alignment agent (C-4) obtained in Example 31 was used, and the alignment state φ of the liquid crystal was confirmed, and the voltage holding ratio and ion density were measured. . The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 which will be described later. &lt;Example 46&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal alignment agent (C-5) obtained in Example 32 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The ion state of the liquid-105-201033249 crystal unit was observed by a polarizing microscope, and the ion density was measured after confirming the voltage holding ratio of the uniform crystal unit without defects. The measurement results of the electron density are shown in Table 1 which will be described later. &lt;Comparative Example 6 &gt; In addition to the use of the liquid crystal alignment agent obtained in Comparative Example 4 (Twisted nematic liquid crystal cell was produced in Example 42, the liquid crystal and the measured voltage holding ratio and the ion density were confirmed. The alignment state of the polarized microscopic unit of $1 was confirmed. For the uniform alignment without defects, the ion density was measured after the voltage holding ratio of the unit. The measurement results of the voltage 傍 density are shown in Table 1 below. Example 14 to Example 16, Example 40 to Example 3, and comparison The voltage holding ratio and the ion density of Example 6 are shown in Table 1. The liquid retention rate and the separation are measured, and the alignment state is observed. The liquid crystal is measured by the liquid crystal: the retention ratio and the ion application 46. Ratio: Measurement result For example, -106- 201033249 [Table i] Liquid crystal alignment agent voltage retention rate "%1 ion density [pC/cm2] 23〇C 60°C 90°C 23〇C 60°C Example Η A-1 99.3 98.7 94.1 10 18 Example 15 A-2 99.3 98.8 94.4 5 11 Example 16 A-3 99.4 99.1 96.7 3 4 Example 40 A-4 99.0 97.2 91.9 40 176 Example 41 A-5 99.3 98.2 93.3 21 127 Example 42 C- 1 99.6 98.0 90.2 6 59 Example 43 C-2 99.8 99.1 96.2 24 42 Implementation Example 44 C-3 99.8 99.3 96.5 45 271 Example 45 C-4 99.6 98.0 90.2 18 155 Example 46 C-5 99.8 99.2 96.2 48 55 Comparative Example 3 B-1 99.1 97.4 86.7 50 256 Comparative Example 6 D-1 99.3 95.9 82.0 185 844 &lt;Example 47&gt; The liquid crystal alignment agent (Α-1) obtained in Example 8 was filtered using a filter of 〇μηα, and then spin-coated on a glass substrate with a transparent electrode, and then placed at 80-c. After drying on a hot plate for 5 minutes, the film was baked at 2301 for 20 minutes, and a polyimide film having a film thickness of 100 nm was obtained. The ultraviolet film of 254 nm having an irradiation amount of 〇J/cm 2 was irradiated onto the coating film through a polarizing plate. On the surface, a substrate with a liquid crystal alignment film is attached. Two substrates with the liquid crystal alignment film are prepared, and a 6 μm distance shifter is dispersed on the liquid crystal alignment film surface of one of the substrates, and then two pieces are combined from a parallel twist of 85 degrees. The alignment direction of the substrate was sealed around the liquid crystal injection port to form an empty cell having a cell gap of 6 μm. Liquid crystal (MLC-2 03, manufactured by Merck) was vacuum-injected into the empty cell at room temperature, and then sealed. The inlet is twisted into the nematic liquid crystal cell. The alignment state of the liquid cell of -107-201033249 was observed by a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 48&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal alignment agent (A-2) obtained in Example 9 was used, and the alignment state of the liquid crystal and the measurement voltage holding ratio and the ion density were confirmed. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 49&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal alignment agent (A-3) obtained in Example 1 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. <Example 50> A twisted nematic liquid crystal was produced in the same manner as in Example 47 except that the liquid crystal alignment agent (A-4) obtained in Example 26 was used. The unit confirms the alignment state of the liquid crystal, and measures the voltage holding ratio and the ion density. Observation of the alignment state of the liquid cell -108 - 201033249 by a polarizing microscope was confirmed as a uniform alignment without defects. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 51&gt; The twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal alignment agent (A-5) obtained in Example 27 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Comparative Example 7 &gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal alignment agent (B-1) obtained in Comparative Example 1 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. . The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 52&gt; The liquid crystal alignment agent (C-1) obtained in Example 28 was filtered using a filter of 1·Ομηι, and then spin-coated on a glass substrate with a transparent electrode, and placed on a hot plate at 8 °C. After drying for 5 minutes and baking at 2 3 01 for 1 hour, a polyimide film having a film thickness of -109 to 201033249 lOOnm was obtained. Ultraviolet rays of 25 4 nm having an irradiation amount of loj/cm 2 were applied to the surface of the coating film via a polarizing plate to obtain a substrate to which a liquid crystal alignment film was attached. Two substrates with the liquid crystal alignment film were prepared, and a 6 μm distance adjuster was dispersed on the liquid crystal alignment film surface of one of the substrates, and the alignment direction of the two substrates was combined under the condition of a parallel twist of 85 degrees, and the liquid crystal injection port was left. The condition is sealed around the 'empty unit with a cell gap of 4μηι. Liquid crystal (MLC-2 00 3, manufactured by Merck) was vacuum-injected into the empty cell at room temperature, and the nematic liquid crystal cell was twisted after sealing the inlet. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 53&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal alignment agent (C-2) obtained in Example 29 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The alignment state of the liquid crystal unit was observed by a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 54&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal alignment agent (C-3) obtained in Example 30 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The alignment state of the liquid cell 110-.201033249 crystal unit was observed by a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 55&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal alignment agent (C-4) obtained in Example 31 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio was measured. Ion density. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After measuring the voltage holding ratio of the liquid crystal cell, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Example 56&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal alignment agent (C-5) obtained in Example 32 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. &lt;Comparative Example 8&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal alignment agent (D-1) obtained in Comparative Example 4 was used, and the alignment state of the liquid crystal was confirmed, and the voltage holding ratio and the ion density were measured. The alignment state of the liquid crystal of -111 - 201033249 was observed by a polarizing microscope, and it was confirmed that the uniform orientation of the liquid was not defective. After the voltage holding ratio of the liquid crystal cell was measured, the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 to be described later. Table 2 shows the measurement results of the voltage holding ratio and the ion density of Examples 47 to 56 and Comparative Examples 7 to 8. [Table 2] Liquid crystal alignment agent voltage retention rate [%] Ion density [pC/cm2] 23 〇 C 60 ° C 90 ° C 23 〇 C 60 ° C Example 47 A-1 99.2 96.4 83.2 151 2056 Example 48 A -2 99.2 94.4 72.2 262 4475 Example 49 A-3 99.3 97.6 87.6 22 1013 Example 50 A-4 99.1 95.2 79.2 617 1779 Example 51 A-5 99.3 98.4 93.2 32 501 Example 52 C-1 98.9 90.9 57.9 1576 8717 Example 53 C-2 98.9 90.4 57.7 1721 9235 Example 54 C-3 98.8 87.3 46.7 2943 12430 Example 55 C-4 97.4 85.3 43.3 1332 7334 Example 56 C-5 99.1 92.78 65.6 625 10720 Comparative Example 7 B- 1 98.6 90.1 64.3 630 5055 Comparative Example 8 D-1 97.0 72.8 18.8 5103 22820 &lt;Example 57&gt; Modulation of polyphthalate resin (E-1) P-PDA 1.50 g (1 3.87 mmol) under nitrogen, DA -B 0.4090 g (1.541 mmol), NMP 1 07 · 47 g and pyridine 2· 8 2 g (3 5.67 mmol) for the base were placed in a 300 mL four-necked flask equipped with a stirring apparatus, and stirred and dissolved. Next, while stirring the diamine solution, 4.83 g (14.86 mmol) of 1,3DMCBDE-C1 was added, and the reaction was carried out for 4 hours under water cooling. The obtained polyphthalate solution was poured into 566 g of water which was stirred, and the precipitated white -112-.201033249 was precipitated again. Subsequently, it was washed once with 566 g of water and then washed once with 566 g of ethanol. Then, it was washed three times with 141 g of ethanol, and dried to obtain 4.92 g of a white polyphthalate resin (E-1) powder. The yield was 87.0%. Further, the molecular weight of the polyglycolate was Mn = 17,828, Mw = 3l, 832. &lt;Example 5 8&gt; The polyphthalate resin powder obtained in Synthesis Example 57 was fractionated in an Erlenmeyer flask. After 2 g of ruthenium, 9.18 g of γ-BL was added, and the mixture was stirred at room temperature for 24 hours to be dissolved. 1.0% by mass of γ-butyrolactone solution of decane coupling agent with 3-glycidoxypropylmethyldiethoxy decane (hereinafter abbreviated as GPS) was added to the solution at 50 ° C. Stir under heating for 24 hours. γ-ΒΖ 2.41 g and BCS 3.41 g were added to the resulting solution, and stirred with a magnetic stirrer for 30 minutes to prepare a polyamidate solution.醯-α, Ν-ω1, Ν-ω2-tri-t-butoxycarbonyl-L-arginine (hereinafter abbreviated as Boc-Arg) 0.0906g (relative to φ 醯) used as a ruthenium promoter The amine ester group 1 molar is 0.1 mole equivalent), added to 5.75 g of the above polyglycolate solution, and stirred at room temperature for 30 minutes to completely dissolve Boc-Arg, thereby obtaining the liquid crystal alignment agent of the present invention (E-la) ). &lt;Comparative Example 9 &gt; The polyphthalate resin powder obtained in Comparative Synthesis Example 2 was dispensed in an Erlenmeyer flask. After 1.04 g of the powder, DMF 9-35 g was added, and the mixture was stirred at room temperature for 24 hours to be dissolved. A GPS oxime mass% γ_butane vinegar solution for use in a decane coupling agent was added to the solution at a temperature of 50 ° C for 24 hours. Y_bl-113-201033249 2.71g and BCS 3.06g were added to the resulting solution, and stirred with a magnetic stirrer for 3 minutes to prepare a polyamidate solution. 0.057 g of Boc-Arg (0.1 mol equivalent relative to the valerate group 1 molar) was added to the ruthenium promoter to 5.42 g of the above polyglycolate solution, and stirred at room temperature for 30 minutes. Boc-Arg is completely dissolved, and a liquid crystal alignment agent (D -1 a ) is obtained. &lt;Example 59&gt; The liquid crystal alignment agent (E-la) obtained in Example 58 was filtered using a filter of Ι.ΟμΓη, and then spin-coated on a glass substrate with a transparent electrode, and then dried on a hot plate at 80 °C. After baking at 230 ° C for 20 minutes for 5 minutes, a polyimide film having a film thickness of 100 nm was obtained. Ultraviolet rays of 254 μm having an irradiation amount of 〇J/cm 2 were applied to the surface of the coating film via a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with the liquid crystal alignment film were prepared, and a 4 μm distance adjuster was spread on the liquid crystal alignment film surface of one of the substrates, and the alignment direction of the two substrates was combined under the condition of parallel rotation of 85 degrees, and then the residual liquid crystal was injected. The conditions of the inlet are sealed around, and an empty cell having a cell gap of 4 μm is produced. Liquid crystal (MLC-2 04 1, manufactured by Merck) was vacuum-injected into the empty cell at room temperature, and the nematic liquid crystal cell was twisted after sealing the inlet. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After measuring the voltage holding ratio of the liquid crystal cell, the ion density was measured, and as a result, the voltage holding ratio was 99.4% at 23 ° C, 98.6% at 60 ° C, 95.3% at 90 ° C, and an ion density of 85 cP/cm 2 at 23 ° C. 60 °C 5 07 cP/cm2 ° -114-201033249 &lt;Comparative Example 1 〇&gt; A twisted nematic liquid crystal cell was produced in the same manner as in Example 59 except that the liquid crystal alignment agent (Da) obtained in Comparative Example 9 was used. The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no defect uniform alignment. After measuring the voltage holding ratio of the liquid crystal cell, the ion density was measured, and as a result, the voltage holding ratio was 9 9 · 2 % at 23 ° C, 9 8 . 1 % at 60 ° C, and 9 4 · 9 at 90 ° C. %, the ion density is 159 cP/cm 2 at 23 ° C, and 6 0 ° CT 644 cP/cm 2 . From the above-mentioned results, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is a liquid crystal alignment film which is excellent in mechanical strength and which does not easily attach a frictional flaw even when a rubbing treatment is not carried out. Further, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is a liquid crystal display element which can maintain a high voltage retention ratio and a low ion density even at a high temperature and has excellent reliability. In addition, when the polarized ultraviolet light is irradiated onto the liquid crystal alignment film of the present invention and the light distribution treatment is performed to impart liquid crystal alignment energy, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be confirmed. It is a liquid crystal display element which has high reliability and high ion density and high reliability while maintaining high temperature. Comparing Example 5 and Comparative Example 1 0, it was confirmed that even if a liquid crystal alignment agent of the present invention is added with a decane coupling agent and other additives, a liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention can be obtained at a high temperature. Liquid crystal display element which has high voltage holding ratio and low ion density and has excellent reliability -115-201033249 [Industrial use possibility] It is obtained by using the liquid crystal alignment agent of the present invention, and is subjected to friction treatment with friction scar and excellent mechanical strength. The liquid crystal alignment film and the liquid crystal alignment film can obtain a liquid crystal display element with less display defects. In the liquid crystal alignment film of the present invention, the liquid crystal alignment element of the present invention is suitable as a liquid crystal alignment for a member of a liquid element, regardless of the alignment treatment method, and has a high voltage retention ratio and a low ion density at a high temperature to have an excellent liquid crystal display element. membrane. Since the polyimine precursor and the polyimine of the present invention contain a protected primary or secondary aliphatic amine, they can be separated from Boc intermolecular crosslinking during firing, thereby providing a polythene having excellent mechanical strength. Amine polyimide membranes are suitable for use in protective films and electronic devices, especially alignment films. Further, since the diamine compound of the present invention has a structure containing a Boc-based or a second-order aliphatic amine, it is most suitable as a precursor for the production of the present polyimine and polyimine, and a liquid crystal alignment raw material using the same. In addition, the specification of the Japanese Patent Application No. 2008-2783 No. 17 filed on Oct. 29, 2008, the entire disclosure of the patent application, and the entire contents of the disclosure are incorporated by reference. It is not easy to use this, and it can be used. The reliability of the crystal display is not B 〇 c based on the film, which is the application of the liquid crystal protection 1 invention.

Claims (1)

201033249 VII. Patent application: 1. A liquid crystal alignment agent characterized by comprising a polyimine precursor having a substituent represented by the following formula (1) or a precursor of the polyimine醯iminated polymer, [Chemical 1] Ch3 —ch3 (1) ch3 11 I3 —A—C—N- R2 (wherein A is a single bond or a divalent organic group, and 1^, 112 and R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). 2. The liquid crystal alignment agent of claim 1, wherein the polyamidene precursor or the ruthenium imidized polymer of the polyimide precursor has a substituent represented by the formula (1) At least one selected from the group consisting of a diamine compound and a tetracarboxylic acid derivative having a substituent represented by the formula (1). 3. The liquid crystal alignment agent of claim 2, wherein the polyamidene precursor or the ruthenium imidized polymer of the polyimide precursor uses all of the diamine compound and the tetracarboxylic acid derivative 2 Up to 100% by mole of a diamine compound having a substituent represented by the formula (1) and/or a tetracarboxylic acid derivative having a substituent represented by the formula (1). 4. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polyimine precursor is a structural unit having the following formula (2), -117 - 201033249 I R40 X-ζ_\ /Μ ο= OR4 Η Ν I b 1 ») γ—ζ -( Η Ν (2 (wherein, Χι is an organic group of (4 + a) valence, Υι is an organic group of (2 + b) valence, Κ 4 is a hydrogen atom or a carbon number of 1 to 4, Z is a structure represented by the above formula (1), and a and b are each an integer of 0 to 4, a + b &gt; 0). The liquid crystal alignment agent of any one of the items 1 to 3, wherein the polyimine precursor is a structure containing a structural unit of the following formula (3), [Chemical 3] Ο 〇 -OR, X 4 (3) R4O-ff &gt;1—NH-Y2—NH— .1 〇Γ (i)c . (wherein X is a tetravalent organic group and γ2 is a (2 + C) valence The organic group 'R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a structure '(; an integer of 1 to 4) represented by the above formula (1). 6. Patent Application Nos. 1 to 3 The liquid crystal alignment agent according to any one of the preceding claims, wherein the polyimine precursor is a structure containing a structural unit represented by the following formula (4), -118- (4) 201033249 [Chemical 4] (2) c COOR4 --CO—X—CO—NH I COOR4 R5—NH— — wherein X is a tetravalent organic group, R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 is a single bond or a divalent organic group having 1 to 20 carbon atoms, and Z is the above The structure represented by the formula (1), c is an integer of 1 to 4). 7. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polyimine precursor is a structure containing a structural unit represented by the following formula (5), [Chem. 5] (Z) COOR4 "-CO-X-CO-NH-d Λ COOR4 '-^ ΝΗ_ (wherein X is a tetravalent organic group, R4 is a hydrogen atom or a carbon number of 1 to 4, Z is a structure represented by the above formula (1), and c is an integer of 1 to 4). A liquid crystal alignment film obtained by baking a liquid crystal alignment agent according to any one of claims 1 to 7 at 150 to 300 ° C. A polyimine precursor comprising a structural unit represented by the following formula (6), -119- 201033249 [Chem. 6] (wherein X is a tetravalent organic group, Y2 is a (2 + c) valence organic group, Z is a structure represented by the following formula (1), and R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; , c is an integer from 1 to 4) I -A-C-N- I r2 o ch3 JL〇--ch3 (1) ch3 (wherein A is a single bond or a divalent organic group, 1, 112 and R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). 10. A polyimine which comprises a structural unit represented by the following formula (7), [Chem. 8] -120- 201033249 (wherein X is a tetravalent organic group, ¥2 is an organic group of (2 + c) valence, Z is a structure represented by the following formula (1), and c is an integer of 1 to 4) C-NI r2 Μ -ο ch3 —ch3 (1) ch3 (wherein a is a single bond or a divalent organic group, and 111, 112 and R3 each independently form a hydrogen atom or have a carbon number of 1 to 20; 1 valent organic base). A polyimine precursor comprising a structural unit represented by the following formula (8), coor4 -CO-X-CO-NH I COOR4 (Z)c-ο r5-nh - (8) (wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 is a carbon number of 1 to 20 a divalent organic group, c is an integer from 1 to 4) I11 I3 -A~C-ISI- I r2 〇ch3 [ο——ch3(1) ch3 (wherein A is a single bond or a two-valent organic The bases, 1^, 112 and R3 are each independently -121 - 201033249 and are represented by a hydrogen atom or a monovalent organic group having a carbon number of 1 to 20. A polyimine which contains a structural unit represented by the following formula (9), (wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), R5 is a divalent organic group having 1 to 20 carbon atoms, and c is an integer of 1 to 4 [Chemical 13] 11 |3 —A—C—N— I R2 o ch3 -IL-o--CH3 (1) ch3 ❹ (wherein A is a single bond or a divalent organic group, and 1^, 112 and R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 13. A polyimine precursor comprising a structural unit represented by the following formula (10), [Chem. 14] Z)c C00R4 I -CO —X—CO—NH C00R4 NH—(10) 122 201033249 (wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), and R 4 is a hydrogen atom or a carbon number of 1 to 4 Alkyl, c is an integer from 1 to 4 [Chem. 15] -A- Ri R3 〇 丨丨丨丨 R2 ch3 —ch3 (1) ch3 (wherein A is a single bond or a divalent organic group, and R3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). A polyimine which contains a structural unit represented by the following formula (11), (wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), and c is an integer of 1 to 4) [Chem. 17] Ri R3 0 II II -A-c —N—^0 r2 ch3 —ch3(1) ch3 -123- 201033249 (wherein A is a single bond or a divalent organic group, and Ri, R2 and R3 are each independently a hydrogen atom or a carbon number of 1 to 20 organic base). 15. A diamine compound which is represented by the following formulas (A) to (F), [Chem. 18] -124 201033249 IV. Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is simple: No -3- 201033249 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (1) (Chemical 1) 11 13 -A-C-N-R2 3 ch3 ο--ch3 ch3 -4-