TW201030056A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Abstract

A liquid crystal aligning agent capable of providing a liquid crystal alignment film which is not susceptible to film separation or chipping during rubbing, has high voltage holding ratio, and does not easily accumulate electrical charges at the initial stage even when a direct current voltage is applied to the liquid crystal cell. The liquid crystal aligning agent contains at least one kind of polymer selected from polyamic acids, each of which is obtained by reacting a diamine component containing a diamine represented by formula [1] with a tetracarboxylic acid dianhydride component, and polyimides obtained by imidizing the polyamic acids. (In the formula, X represents a single bond, an alkylene having 1-3 carbon atoms, -OCH2-, -CH2OCO-, -NHCO-, -CONH- or -COOCH2-; Y represents an oxygen atom or a sulfur atom; and any hydrogen atom in the five-membered ring can be substituted by an alkyl group having 1-5 carbon atoms.)

Description

201030056 VI. Description of the Invention [Technical Field] The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element for use in a liquid crystal display element. [Prior Art] At present, a liquid crystal alignment film of a liquid crystal display element mainly uses a liquid crystal alignment treatment agent which is mainly composed of a solution of a polyfluorene imine or a polyacrylamide precursor such as poly Φ lysine or the like. A so-called polyimine-based liquid crystal alignment film which is formed later. The liquid crystal alignment film not only controls the alignment state of the liquid crystal but also affects the characteristics of the liquid crystal display element. In particular, as the liquid crystal display element is highly refined, it is important to suppress the contrast reduction of the liquid crystal display element and to reduce the characteristics of afterimage development. In the polyimine-based liquid crystal alignment film, the time period until the afterimage of the DC voltage disappears is short, and for example, a polyamine or a polyamido acid containing a quinone is used, and a specific structure is used. (for example, refer to Patent Document 1), or a liquid crystal alignment treatment agent containing a soluble polyimine containing a specific diamine such as a pyridine skeleton (see, for example, Patent Document 2) It is already known. Further, in the polyimine-based liquid crystal alignment film, the voltage holding ratio is high, and the time until the residual image due to the DC voltage disappears is short, for example, in addition to poly-proline or a quinone imidized polymer thereof. Liquid crystal alignment using a compound containing a very small amount of a compound containing one carboxylic acid group in the molecule, a compound containing one carboxy-5-201030056 acid anhydride group in the molecule, and a compound having one tertiary amino group in the molecule The treatment agent (for example, refer to Patent Document 3) is known. CITATION LIST Patent Literature [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Immediately] [The problem to be solved by the invention] Up to now, the solution to the afterimage development of the liquid crystal panel has, for example, shortened the time until the afterimage disappears, but this countermeasure is still insufficient. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide film peeling or chip resistance during rubbing, high voltage holding ratio, and low initial voltage accumulation even when a direct current voltage is applied to a liquid crystal cell. A liquid crystal alignment treatment agent for a liquid crystal alignment film. Means for Solving the Problems The inventors of the present invention have completed the present invention in order to achieve the above object. In other words, the present invention has the following inventive requirements. (a liquid crystal alignment treatment agent characterized in that it contains a polyamine acid obtained by reacting a diamine component containing a diamine having the following formula π] of 201030056 with a tetracarboxylic dianhydride component, and the polyfluorene is obtained. a polymer of at least one of a group of polyimines obtained by ruthenium imidization of aminic acid, [Chemical Formula 1]

〇 (wherein 'X represents a single bond, an alkylene group having a carbon number of 1 to 3,

-OCH2-, -CH20C0-, -NHCO-, -CONH-, or -COOCH2-, Y represents an oxygen atom or a sulfur atom, and any hydrogen atom of the five-membered ring may be substituted with an alkyl group of 1 to 5 carbon atoms. ). (2) The liquid crystal alignment treatment agent according to the above item (1), wherein γ of the formula [丨] is an oxygen atom. (3) The liquid crystal alignment treatment agent according to the above item (1), wherein γ of the formula [] is a sulfur atom. The liquid crystal alignment treatment agent according to any one of the above items (1) to (3), wherein X of the formula [1] is -CH2OCO-, -NHCO-, or -COOCH2-. (5) The liquid crystal alignment treatment agent according to the above item (1), wherein X of the formula [丨] is -CH2OCO-'-NHCO- or -COOCH2-, and Y is an oxygen atom. (6) The liquid crystal alignment treatment agent according to any one of the items (1) to (5), wherein any one of the hydrogen atoms of the five-membered ring of the formula [1] is substituted with a methyl group. (7) A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of the above (1) to (6). (8) A liquid crystal display element characterized by comprising the 201030056 liquid crystal alignment film of the above (7). (9) A diamine characterized by the following formula [2], [Chemical 2]

(Any hydrogen atom of the furan ring may be substituted by an alkyl group having 1 to 5 carbon atoms). (10) The diamine of the above item (9), wherein any hydrogen atom of the furan ring is substituted by a methyl group. (11) A polyimine which is characterized in that the polyamine contained in a diamine component containing the diamine of the above (9) or (10) is reacted with a tetracarboxylic dianhydride component, or the poly The proline acid is obtained by hydrazylation. In the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film which is excellent in film peeling resistance during cutting, has high cutting resistance, and has a high voltage holding ratio, and which does not easily generate initial charge accumulation even when a DC voltage is applied to the liquid crystal cell. This liquid crystal alignment film can produce a liquid crystal panel having good characteristics. According to the liquid crystal alignment treatment agent of the present invention, the polyamine acid obtained by reacting a diamine component containing a diamine of the following formula [1] with a tetracarboxylic dianhydride component, and the polymerization are contained. The phthalic acid is a liquid crystal alignment treatment agent for at least one of the polyimine obtained by hydrazylation. By using this diamine ' -8 - 201030056, even in the rubbing treatment necessary for the liquid crystal alignment treatment, the film peeling and the cutting at the time of rubbing can be reduced, and the obtained liquid crystal alignment film has a high voltage holding ratio, and even for the liquid crystal cell When a DC voltage is applied, initial charge accumulation is less likely to occur. <Diamine of the formula [1]> The method for synthesizing the diamine represented by the formula [1] is not particularly limited, and for example, it may be a general formula obtained by combining φ into a dinitro compound represented by the following formula [S1]. The method synthesizes a method in which a nitro group is converted into an amine group. [Chemical 3]

[S1] The above formula Π) and the formula X in the formula [S1] represent a single bond, and the number of carbon atoms is 1 to 3, -OCH2-, _CH2〇CO-, -NHCO-, -CONH-, or - COOCH2-. The γ in the above formula [1) and formula [si] represents an oxygen atom or a sulfur atom. Any one of the five-membered ring of an oxygen atom (hereinafter also referred to as a furan ring) or a five-membered ring of γ as a sulfur atom (hereinafter also referred to as a thiophene ring) may be substituted with an alkyl group having 1 to 5 carbon atoms. . The number of substituents of the furan ring or the thiophene ring is preferably 〇 〜 2, more preferably unsubstituted. Thereby, better frictional resistance can be obtained. In the above formula 及] and the formula [S1], the position at which the furan ring or the thiophene ring is bonded to hydrazine is not particularly limited, and is preferably a position of 2 or 3 positions. 201030056 A liquid crystal alignment film obtained by using X as a -CH2OCO- or -NHCO-diamine increases the voltage holding ratio when used as a liquid crystal panel. Further, when a diamine wherein X is -CH2OCO- is used, a liquid crystal panel excellent in liquid crystal alignment property and in which electric charge is not easily accumulated can be obtained, which is preferable. In the diamine represented by the formula [1], the position of each substituent on the benzene ring is not particularly limited. From the viewpoint of the alignment of the liquid crystal when it is a liquid crystal alignment film. The positional relationship of the two amine groups is preferably a meta or para position, and more preferably from the viewpoint of improving the polymerization reactivity or the solubility of the obtained polyglycolic acid or polyimine in an organic solvent. When the positional relationship of the two amine groups is meta, in other words, the position of X is preferably 4 or 5 in the case of the '1,3-diaminobenzene structure', particularly from the effect of enhancing the nucleophilicity of the amine group or The point of easy synthesis is better than the position of 5. In the diamine represented by the formula [1], the position of the X bond in the ciS-diene ring (hereinafter also referred to as a furan ring or a thiophene ring) is not particularly limited, and from the viewpoints of raw material availability, reactivity, and the like, The combination is appropriately selected in accordance with the purpose. Specific examples of the case where Y is an oxygen atom (for the furan ring) are as follows, but are not limited thereto. [Chemical 4]

-10 201030056 (X in the above formula represents a single bond, an alkylene group having a carbon number of 1 to 3, -OCH2-, -CH20C0-, -NHCO-, -CONH-, or -COOCH: represents a carbon number of 1 The alkyl group of ~5 represents an integer of 〇~3. In the above formula [Τ1]~[[6], X is preferably -CH2OCO-, or -NHCO-, and R is preferably a carbon number of 1 to 3. The alkyl group and the η system are preferably an integer of 1. Further, in the above formula, from the viewpoints of solubility of polyglycine or polyimine, liquid crystal alignment, friction resistance, and accumulated charge (hereinafter referred to as RDC), it is preferably a formula [Τ2] or a formula [Τ5]. Structure. Among them, a structure of the formula [Τ2] or the formula [Τ5] is preferred, X is -CH2OCO- or -NHCO-, R is an alkyl group having 1 to 3 carbon atoms, and an integer of η is 〇. When the linking group X is -CH2OCO- or -NHCO-, the voltage holding ratio is increased, and in particular, the -CH2OCO-diamine liquid crystal is excellent in alignment, which is preferable. Specific examples of the case where Y is a sulfur atom (in the case of a thiophene ring) are as follows, but this limitation. β [化5]

-, R 〇 or soluble, also known as or 1 diamine, not

-,R

(X in the above formula represents a single bond, an alkylene having a carbon number of 1 to 3: -OCH2-, -CH2OCO-, -NHCO-, -CONH-, or -COOCH-11 - 201030056 means a carbon number of 1~ 5 alkyl, η represents an integer of 0 to 3) In the above formula [U1]~S[U6], X is preferably -CH2OCO- or -NHCO-, and R is preferably an alkyl group having 1 to 3 carbon atoms. , η is preferably an integer of 0 or 1. Further, in the above formula, from the viewpoints of solvent solubility, liquid crystal alignment, friction resistance, and accumulated charge (hereinafter also referred to as RDC) of polyacrylic acid or polyimine, the formula [U2] or formula [preferably] The structure of U5]. Among them, a structure of the formula [U2] or the formula [U5] is preferred, X is -CH2OCO- or -NHCO-, R is an alkyl group having 1 to 3 carbon atoms, and η is an integer of 0 or 1 @. When a diamine having a linking group X of -CH2OCO- or -NHCO- is used, the voltage holding ratio is increased, and in particular, when a diamine of -CH2OCO- is used, liquid crystal alignment is particularly excellent, which is preferable. <Synthesis of Diamine> The specific diamine compound of the present invention is obtained by synthesizing a dinitro group represented by the formula [S1], reducing a nitro group, and converting it into an amine group. The method for reducing the dinitro compound is not particularly limited, and palladium-carbon, platinum oxide, @Rani nickel, platinum black, lanthanum-alumina, and platinum sulfide carbon are usually used as a catalyst, and ethyl acetate is used. A method of carrying out a solvent such as toluene, tetrahydrofuran, dioxane or an alcohol by hydrogen, hydrazine, hydrogen chloride or the like. X of the following formula [S1] represents a single bond, an alkylene group having 1 to 3 carbon atoms, -〇CH2-, -CH2OCO-, -NHCO-, -CONH-, or -COOCH2-, and Y represents an oxygen atom. Or a sulfur atom, any hydrogen atom of the five-membered ring may be substituted with an alkyl group having 1 to 5 carbon atoms. -12- 201030056 化2N-Q [S1] ^N〇2 The synthesis method of the dinitro group differs depending on the bonding group. When X is -CHsCOO-, for example, a dinitrobenzene can be obtained by subjecting dinitrobenzyl alcohol to a condensation reaction with furancarboxylic acid or thiophenecarboxylic acid. The condensation method is not limited to φ. The dinitrobenzene [S4] can be obtained by reacting dinitrobenzyl alcohol [S2] with residual acid chlorine [S3] in the presence of a base. Further, a method of reacting an alcohol with a carboxylic acid in the presence of a dehydrating condensing agent.

[Chemistry 7]

Base Solvent

When X is -NHCΟ-, the dinitro group can be obtained, for example, by subjecting dinitroaniline to condensation reaction with furancarboxylic acid or thiophenecarboxylic acid. The condensation method is not particularly limited, and a dinitrobenzene [S 7] can be obtained by reacting dinitroaniline [S 5] with a carboxylic acid chloride [S 6] in the presence of a base. Other examples include a method of reacting an amine with a carboxylic acid in the presence of a dehydrating condensing agent, and the like. -13- 201030056 [Chem. 8] NH, id + P „ HN-^ ^jfCOCI Base Solvent 〇2ΝΛΛΝ〇2 [S5] [S6] [S7] X is - COOCH2 - for example by dinitrobenzoic acid with furan A condensation reaction can be obtained by methanol or thiophene methanol. The condensation method is not particularly limited, and a dinitroso group [S 1 0] can be obtained by reacting dinitrobenzoic acid chloride [S8] with an alcohol [S9] in the presence of a base. For example, there is a method of reacting an alcohol with a carboxylic acid in the presence of a dehydrating condensing agent, etc. [Chemical 9] o2n COCIJ0L ^^Ν〇2

Base Solvent

02N

[S8] [S9] [S10]

A side chain to which a furan ring (or a thiophene ring) is attached may be obtained by using a reagent in which an alkyl group is added to a furan ring or a thiophene ring or a pre-alkyl group addition. <Diamine component> The diamine represented by the above formula [1] can be obtained by reacting with a tetracarboxylic dianhydride to obtain a poly-proline, and the polyamine can be imidized to obtain a polyazide. amine. In the present invention, the diamine component used in the synthesis of the polyamic acid may be only a diamine represented by the formula -14 - 201030056 [1] or a combination of one or more selected from the other diamines. The diamine represented by the formula [1] as a diamine component can improve the solubility of the obtained polylysine and the polyamidimide of the polyamidamine in organic solubility. Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent containing the polyamic acid or the polyimine is excellent in friction resistance, high in voltage holding ratio, and a direct current voltage is applied to the liquid crystal cell, and the initial φ charge is less likely to occur. Accumulate. In order to obtain such a characteristic, the diamine represented by the formula [1] is preferably from 10 to 100 mol%, more preferably from 20 to 100 mol%, more preferably from 20 to 100 mol%, particularly preferably ΜΜΟΟιηοΙ, of the diamine component used for the synthesis of the polyamic acid. %. Among the above diamine components, the diamine used in combination with the diamine represented by the formula [丨] is not particularly limited. Specific examples of such a diamine are as follows. The alicyclic diamine is, for example, anthracene, heart diaminocyclohexane, hydrazine, 3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4,-diamino-3 , 3,-dimethyl monocyclohexylamine, isophorone diamine, and the like. ® scented aromatic amines such as 0-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diamine Toluene, 3,5-diamino-N,N-dipropylaniline, 2,4-diamino-N,N-diallylaniline, 1,4-diamino-2-methoxy Benzobenzene, 2,5•diamino-p-xylene, anthracene, 3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4,diamino-2,2'-dimethyl linked, 4,4'-diaminodiphenyl Methane, 3,3,-diaminodiphenylmethyl, 3,4'-monoaminodiphenylmethane, 4,4'-diamino-3,3'dimethyldiphenylmethane, 2,2'-ylindole, 4,4'-diaminopurine, 4,4'-diamino-15-201030056 diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4' -diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminobenzophenone, 1 , 3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5 -bis(4-aminophenoxy)benzene Formic acid, 4,4'-bis(4-aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4 -aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)benzene Grinding, bis[4-(4-aminophenoxy)phenyl]indole, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-bis(4-amino Phenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2- Bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5 -diaminonaphthalene, 1,5-diaminoguanidine, 1,3-diaminoguanidine, 1,6-diaminoguanidine, 1,8-diaminoguanidine, 2,7-diamine芴, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl) Heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)decane, 1,1〇-bis(4-aminophenyl)anthracene Alkane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy) Octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane-1, 3-Diester, bis(4-aminophenyl)butane-1,4-dicarboxylate, di-16-201030056 (4-aminophenyl)pentane-1,5-dicarboxylate, Bis(4-aminophenyl)hexane_i,6-diester, bis(4-aminophenyl)heptane-1,7-diester, bis(4-aminophenyl) octane Alkenyl-1,8-diester, bis(4-aminophenyl)decane-1,9-diester, bis(4-aminophenyl)decane-1,10-diester, ι,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5 - bis[4-(4-aminophenoxy)phenoxy] Alkane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy) φ phenoxy]heptane 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]decane, 1 , 10-bis[4-(4-aminophenoxy)phenoxy]decane, and the like. Heterocyclic diamines are, for example, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodiphenyl And furan, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminophenyl)- 1,3,4-oxadiazole and the like. The aliphatic diamines are, for example, 1,2-diaminoethane, 1,3-diaminopropane, I,4,diaminobutane, I,5-diaminopentane, 1,6 -diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,3 -diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, I ,7·diamino-4,4·dimethylheptane, 1,7-diamino-3·methylheptane, 1,9-diamino-5-methylheptane, ι,ΐ2 -diaminododecane, anthracene, 18.diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like. The aromatic-aliphatic diamine has, for example, a diamine represented by the formula Π 1 ]. -17- 201030056 h^N—Ar—^—NH—R2 [11] The Ar in the above formula represents a phenylphenylnaphthyl group, and the Ri is a carbon number i~5. Is a hydrogen atom or a methyl group. Specific examples of the diamine represented by the formula [11] include 3-aminobenzylamine, 4-amino benzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenylethylamine, 3-(3-aminopropyl) Aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminobutyl) Aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5.amine Benido)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-(6- Aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, etc., but not Limited to this. When the diamine represented by the formula [11] is used in combination with the diamine represented by the formula [1], the obtained polylysine or polyimine (hereinafter referred to as a polymer) can be further dissolved in an organic solvent. When it is used as a liquid crystal alignment film, it is preferable because it is excellent in liquid crystal alignment. When diamine (hereinafter also referred to as a tilted diamine) which expands the pretilt angle of the liquid crystal described later is used, the effect of further increasing the pretilt angle of the liquid crystal is obtained. Therefore, in order to obtain a pretilt angle of the same size, a large pretilt angle can be obtained even if the amount of the tilted diamine used is reduced. Further, it is expected to improve the printability of the liquid crystal alignment agent. -18 - 201030056 The preferred content of the diamine represented by the formula [11] is 10 to 80 mol%, more preferably 20 to 70 mol%, based on the diamine component. A diamine (slanted diamine) which can expand a pretilt angle of a liquid crystal, for example, a long chain compound, a perfluoroalkyl group, an aromatic cyclic group, a substituent of a combination of an aliphatic ring group, a diamine such as a steroid skeleton group, or the like . These can be used in combination with the diamine represented by the formula [1]. Specific examples of the diamine having such a substituent are listed below, but φ is not limited thereto. In the formula [13] to the formula [38] exemplified below, an integer of 5 to 20 is shown, and k is an integer of 1 to 20.

Mk11] has a basal and suitable diamine. This is a j-series h2 nh2 4 0(CH2)j〇H3 [12] H less l_ nh2 nh2 h2n_

_ a __. ^ """^~^-〇(CH2^H3 兮 [13] <CH2>kCH3 [14]

(CH2)lPH3 [15] -19- 201030056 [Chemical 12] nh2h2-^^N Vo ^-〇(CH2)kCH3 Ο H2 H2NY^A〇,C^^O(CH2)kCH3 [17] NH2 0(CH2 )kCH3

[1S]

0(CH2)kCH3 [Chemical 13] nh2 (CH2)kCH3 [19] H2N—

HjM— ^〇-〇~〇-(cH2)kCH3 RO] O~0~0~ (CH2)kCH3 [21]

-20- 201030056 [Chem. 14]

(CH2)kCHb [22]

[2 sentences [化15] h2n νη2 V (called Η2Ν^_, [27] />~ΝΗ.

H2N

Ο 0:9 0(CH2)kCH3 [28] η2ν·

ΝΗ 2 [30] 乂ΟτΟγ OCF3 νη2Η2Ν-^^-°-^^—(^)—(CH2)kCH3 [31] -21 - 201030056 [Chem. 16]

[33]

H2N

[35] [34] (CHa^OHj

[Π化]

Among the "diamines of the batch", the diamine liquid crystal of the formula [1 2 ] is excellent in the alignment property of the liquid crystal. The diamine-based pretilt angle of the formula [I9] to [26] can be very high. Therefore, it is suitable for an aligning film for opaque CB (Optically Compensated Bend) (alignment film for OCB under -22-201030056), vertical alignment An alignment film for a mode liquid crystal (hereinafter referred to as an alignment film for VA). For example, when the alignment film of the TN liquid crystal (pretilt angle is 3 to 5°), the content of the diamine of the formula [12] is preferably 10 to 30 mol% of the entire diamine component, and the alignment film for OCB or the alignment film for VA. When the pretilt angle is 10 to 90°, the content of the diamine of the formula [19] to [26] is preferably 5 to 40 mol% of the entire diamine component, but is not limited thereto. φ In consideration of the balance between the solubility of polyphthalic acid or polyimine used in the liquid crystal alignment agent of the present invention, the alignment of liquid crystal, the tilt angle, the voltage holding ratio, and the accumulated charge, for example, When the diamine component represented by the formula [11] and the formula [12] is polymerized, the preferred ratio of the respective diamine components is expressed by the molar ratio, preferably from 1 to 50% (formula [ 1]) / 20 ~ 80% (form [11]) / 10 ~ 30% (form [12]), more preferably 20 ~ 40% / 3 0 ~ 50% / 10 ~ 3 0 〇 / 〇, but not Limited to this.四 <tetracarboxylic dianhydride component> The polycarboxylic acid or polyimine which is required for the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as the tetracarboxylic dianhydride component which reacts with the above diamine component. In other words, it is possible to use two or more kinds of tetracarboxylic dianhydrides of one type of tetracarboxylic dianhydride or hydrazine. In the liquid crystal alignment agent of the present invention, the tetrahydro acid dianhydride which reacts with the diamine component is preferably a tetrahydro acid having an alicyclic structure or an aliphatic structure, from the viewpoint of further increasing the voltage holding ratio of the liquid crystal cell. Diacid anhydride. The four-residual acid dianhydride having an alicyclic structure or an aliphatic structure is, for example, -23-201030056 1,2,3,4-cyclobutanine tetraresidic acid di-hepatic, 1,2-dimethyl-1,2,3 , 4-cyclobutylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 -naphthylsuccinic dianhydride, [4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride], 1, 2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-di Cyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6 -carboxylic acid dianhydride, tricyclo[4.2.1.〇2,5]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride,hexacyclo[6_6.0.12 , 7.03, 6.19, 14.010, 13] hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, and the like. Among them, in particular, when 1,2,3,4-cyclobutanetetracarboxylic dianhydride is used, an alignment film having excellent liquid crystal alignment property can be obtained, which is preferable. When an aromatic tetracarboxylic dianhydride is used, the liquid crystal alignment property can be improved, and the accumulated charge of the liquid crystal cell can be quickly eliminated. The aromatic tetracarboxylic dianhydride is, for example, pyromellitic dianhydride, 3,3',4,4,-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Anhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4-diphenyl Ketone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4.dicarboxyphenyl) succinic anhydride, 1,2,5,6-naphthalenetetracarboxylic acid Diacetic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like. Among them, pyromellitic dianhydride is preferred. Considering the balance of the solubility of the obtained polyaminic acid or polyimine, the alignment of the liquid crystal, the voltage holding ratio, and the accumulated charge, the tetracarboxylic acid having an alicyclic structure or an aliphatic structure of -24 to 201030056 The use ratio of the acid dianhydride to the aromatic tetracarboxylic dianhydride is expressed by the former/the latter molar ratio, preferably 90/10 to 50/50, more preferably 80/20 to 60/40 ° &lt;polymerization Reaction&gt; In the present invention, the polymerization reaction method of the tetracarboxylic dianhydride component and the diamine component is not particularly limited. In general, the polymerization φ reaction is carried out by mixing in an organic solvent to obtain a poly-proline which can be converted into a polyimine by dehydration ring closure. A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, for example, a solution in which a diamine component is dispersed or dissolved in an organic solvent, and the tetracarboxylic dianhydride component is directly or dispersed or dissolved in a solution. In the method of adding an organic solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, or a method of mutually adding a tetracarboxylic dianhydride and a diamine component, or the like. Further, when the tetracarboxylic dianhydride or the diamine is composed of a plurality of compounds, the plurality of components may be mixed in advance to carry out a polymerization reaction, or the polymerization may be carried out in sequence. The temperature at which the tetracarboxylic dianhydride component and the diamine component are polymerized in an organic solvent is usually 〇 150 ° C, preferably 5 to 100 ° C, more preferably 10 to 80 ° C. At higher temperatures, the polymerization reaction ends quickly, but when it is too high, high molecular weight polymers are sometimes not obtained. The polymerization reaction can be carried out at any concentration. However, when the total concentration of the tetracarboxylic dianhydride component and the diamine component is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction solution is too high. Difficult, because -25- 201030056 The total concentration is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the polymerization reaction is carried out at a high concentration, and thereafter an organic solvent may be added. The organic solvent used in the above polymerization reaction is not particularly limited as long as it is a polylysine which can be produced by dissolution. Specific examples thereof are N,N'-dimethylformamide, guanidine, Ν'-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, oxime-methyl Caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl maple, hexamethyl yam, yttrium-butyrolactone, 1,3-dimethylimidazolidinone and the like. These can be used alone or in combination. Even if it is a solvent which does not dissolve poly-proline, it can be mixed with the above-mentioned solvent in the range which does not isolate|separate the produced poly- amic acid. Further, since the water in the organic solvent hinders the polymerization reaction and also causes hydrolysis of the produced polylysine, the organic solvent is used as far as possible for dehydration. The ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization of polylysine is expressed by a molar ratio, preferably 1:0.8 to 1:1.2, and the molar ratio is closer to 1:1. The greater the molecular weight of polylysine. Controlling the molecular weight of the polyamine can adjust the molecular weight of the resulting polyimine after the imidization. The molecular weight of the polyaminic acid or the polyimine of the present invention is not particularly limited, and is contained in the liquid crystal alignment treatment agent, from the viewpoint of the strength of the obtained coating film and the ease of handling as a liquid crystal alignment treatment agent. The average molecular weight means preferably 2,000 to 200, 〇00, more preferably 5,000 to 50,000. &lt;Synthesis of Polyimine&gt; The polyimine used in the liquid crystal alignment treatment agent of the present invention is a polyimine which is arniminated by the above-mentioned -26-201030056 polyamine. The ruthenium imidization of polyglycolic acid is carried out in an organic solvent in the presence of a basic catalyst and an acid anhydride by stirring for 1 to 100 hours. The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine or the like. Among them, pyridine has a moderate basicity required for carrying out the reaction, and therefore is preferred. Further, the acid anhydride may, for example, be acetic anhydride, trimellitic anhydride, benzene tetracarboxylic anhydride Φ or the like. Among them, acetic anhydride is preferred because the purification of the obtained polyimine is easy after the imidization of hydrazine. As the organic solvent, the solvent used in the polymerization of the aforementioned polyaminic acid can be used. The imidization ratio of the polyimine can be controlled by adjusting the amount of the catalyst, the reaction temperature, the reaction time, and the like. The amount of the alkaline catalyst at this time is preferably from 0.2 to 10 moles, more preferably from 0.5 to 5 moles, per mole of the amidoxime group. The amount of the acid anhydride is preferably from 1 to 30 moles, more preferably from 1 to 10 moles, per mole of the amidate group. The reaction temperature is preferably from -20 ° C to 250 ° C, more preferably from 0 ° C to 180 ° C. φ The ruthenium imidization ratio of the polyimine used in the liquid crystal alignment treatment agent of the present invention is not particularly limited, but the ruthenium imidation ratio is preferably 40 from the reason that a liquid crystal alignment film having a higher voltage retention ratio can be obtained. More than %, more preferably 60% or more, and particularly preferably more than 80%. In the solution of the polyimine obtained as described above, since the catalyst or the like after the addition remains, it is preferred to use the polyimine after the liquid crystal alignment agent is recovered and washed. The recovery of the polyimine is carried out by stirring the solution of the ruthenium iodide into a stirred weak solvent to precipitate the polyimine. The weak solvent at this time -27- 201030056 Examples include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like. This weak solvent can also be used for the washing of the recovered polyimine. The polyimine thus recovered and washed can be dried at normal temperature or under reduced pressure at normal temperature or under reduced pressure. This operation can also be carried out for the aforementioned polylysine. For example, when the liquid crystal alignment agent does not contain a solvent for polymerization of poly-proline, or when unreacted monomers or impurities in the reaction solution are to be removed, the above-described precipitation recovery and purification may be carried out. &lt;Liquid Crystal Alignment Treatment Agent&gt; The liquid crystal alignment treatment agent of the present invention contains a coating liquid selected from at least one of the polyamic acid and the polyimine obtained as described above. The production example is that the reaction solution of the above polyamic acid or polyimine is directly or diluted, or the reaction liquid is re-dissolved in an organic solvent by precipitation. In the step of diluting or redissolving, the solvent composition for controlling the coatability of the substrate or the addition of an additive for improving the film properties can be adjusted. It is also possible to mix or add other resin components to the polyimine solution or the polyaminic acid solution of the above different structure. The organic solvent to be used in the above-mentioned dilution or redissolution step is not particularly limited as long as it is a polymer to be dissolved. Specific examples thereof are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N- Ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl argon, r-butyrolactone, 1,3-dimethyl-imidazole Linoleone and the like. Among them, -28-201030056 is preferably N-methyl-2-indolyl ketone, N-ethyl-2-indole fluorenone, iota, 3-dimethyl-imidazolidinone, γ-butane ester. These may be used alone or in combination of two or more. The solvent used for controlling the applicability of the liquid crystal alignment agent to the substrate is, for example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate , ethylene glycol, 1-methoxy-2-propanol, ethoxylated 2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, two Ethylene glycol diethyl ether, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2_acetate Dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents also contain a solvent which cannot dissolve polyphosphoric acid or polyimine alone, but may be mixed with the liquid crystal alignment agent of the present invention insofar as the polymer does not precipitate. In particular, when a solvent having a low surface tension is appropriately mixed and applied to a substrate, the uniformity of the coating film can be improved, and φ can be suitably applied to the liquid crystal alignment treatment agent of the present invention. Among them, in particular, from the viewpoint of solubility of polyimine, butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether, and diethylene glycol diethyl ether are preferred. Additives for improving coating film properties include, for example, 3-aminopropylmethyldimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, A decane coupling agent such as aminoethylaminomethylmethyl)phenethyltrimethoxydecane. The adhesion to the coating film of the substrate can be improved by adding these decane coupling agents. However, when too much is added, polyglycine or polyimine or the like tends to aggregate. Therefore, the content of the decane coupling agent is preferably 〇·5 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the polyamine -29-201030056 acid or polyimine. The solid content concentration of the liquid crystal alignment agent of the present invention can be appropriately changed depending on the thickness setting of the liquid crystal alignment film to be formed, and is preferably 1 to 10% by mass. When the amount is less than 1% by mass, it is difficult to form a uniform and defect-free coating film. When the content is more than 10% by mass, the storage stability of the solution may be deteriorated. Further, the solid fraction refers to a solvent in which a solvent is removed from the liquid crystal alignment treatment agent. The concentration of the polyamic acid or the polyimine used in the liquid crystal alignment agent of the present invention is not particularly limited, and is preferably 1% by mass or more, and more preferably 3% by mass or more from the viewpoint of the characteristics of the obtained liquid crystal alignment film. , particularly preferably 5 mass% or more. The liquid crystal alignment treatment agent obtained above is preferably filtered before being applied to a substrate. &lt;Liquid crystal display element&gt; The liquid crystal alignment treatment agent of the present invention is applied onto a substrate, dried, and fired to form a coating film, and the coated surface is rubbed to be used as a liquid crystal alignment film for rubbing. Further, it can also be used as a liquid crystal alignment film or a light alignment film for VA (for vertical alignment) which is not rubbed. The substrate to be used in this case is not particularly limited as long as it is a transparent substrate. A plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used, and a substrate such as an ITO electrode for driving a liquid crystal can be used. It is preferred from the standpoint of simplification. Further, in the case of a reflective liquid crystal display element, it is only a single-sided substrate, and an opaque such as a germanium wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode. -30-201030056 The coating method of the liquid crystal alignment agent is, for example, a spin coating method, a printing method, an inkjet method, or the like. From the viewpoint of productivity, the gravure printing method is widely used in the industry, and the liquid crystal alignment treatment agent of the present invention is also applicable. The drying step after the application of the liquid crystal alignment agent is not necessarily required, but the drying step is preferably carried out when the substrate is not fixed, or when the substrate is not fixed, or is not immediately baked after coating. The drying is not particularly limited as long as the substrate is conveyed or the like, and the shape of the coating film is not deformed, and the solvent is evaporated. The specific example is a method of drying on a hot plate of 50 to 150 ° C, preferably 80 to 120 ° C, for 0.5 to 30 minutes, preferably 1 to 5 minutes. The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of 100 to 3 50 ° C, preferably 150 ° C to 300 ° C, more preferably 180 ° C to 2 5 0 ° C. . Further, when the liquid crystal alignment agent contains a proline group, the conversion ratio of the proline to the quinone is changed by the firing temperature, but the liquid crystal alignment agent of the present invention does not necessarily need to be 100. %醯亚# Amination. When the thickness of the coating film after firing is too thick, power consumption of the liquid crystal display element is disadvantageous. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 10 to 200 nm, more preferably 50. ~l〇〇nm. As described above, the rubbing treatment of the coating film surface formed on the substrate can use an existing friction device. The material of the rubbing cloth at this time is, for example, cotton, raw silk, nylon, or the like. The substrate to which the liquid crystal alignment film obtained by the above method is formed is a liquid crystal cell as a liquid crystal display element by a known method. When one example of liquid crystal cell production is cited, -31 - 201030056 Generally, a spacer of preferably 1 to 30 μm, more preferably 2 to 10 μm, is clamped to a substrate on which a liquid crystal alignment film is formed, and the rubbing direction is 0 to 2 7 At any angle of 0°, a method of fixing the periphery with a sealant and injecting the liquid crystal to perform sealing is provided. The method of sealing the liquid crystal is not particularly limited. For example, there is a vacuum method in which a liquid crystal cell after production is decompressed, a vacuum method in which a liquid crystal is injected, and a dropping (ODF) method in which a liquid crystal is dropped and then closed. The liquid crystal display element thus obtained is suitable for use in various liquid crystal display elements, STN liquid crystal display elements, TFT liquid crystal display elements, OCB liquid crystal display elements, liquid crystal display elements of transverse electric field type (IPS), vertical alignment (VA) liquid crystal display elements, and the like. Display element of the mode. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of 3,5-diaminobenzylfuran-2-carboxylate In a 500 mL (ml) three-necked flask, 25.0 g of 1,3-dinitrobenzyl alcohol and 2-furancarboxylic acid group were added. 10.5 mL of chlorine and 3 mL of tetrahydrofuran. Further, 9.0 mL of pyridine was added dropwise, and the mixture was stirred at room temperature for 25 hours. After the completion of the reaction, 50 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated sodium hydrogen carbonate and brine. Subsequently, anhydrous magnesium sulfate was added to the organic layer to carry out dehydration drying. After filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized using tetrahydrofuran/hexane-32-201030056 = 1/3 (volume ratio, the same below) to obtain 27.5 g of a white solid (yield: 93%). The results of 1H-NMR measurement of this milky white solid are shown below. From this result, it was confirmed that the obtained solid was the intended dinitro compound. Further, 1H-NMR refers to a nuclear magnetic resonance spectrum of a hydrogen atom in a molecule. *H NMR (400 MHz « CDC13): 59.04 (t,lH) » 8.66-8.63 (m,2H), 7.65 (dd,lH),7.32 (dd,lH),6.58 (dd,lH),5.53 (s , 2H)

[Chem. 18]

Next, 3.8 g of a dinitro compound 2, a platinum/carbon (mass ratio of 1/1 Torr, the same below), 2.4 g of methanol and 23.9 g of methanol were added to a 500 mL four-necked flask, and the mixture was stirred for 43 hours under a hydrogen atmosphere. After the completion of the reaction, the mixture was filtered through Celite, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using isopropyl alcohol to give 16.1 g of pale orange solid (yield: 85%). The results of 1 Η-NMR measurement of this pale brown solid are shown below. From this result, it was confirmed that the obtained pale orange solid was the intended diamine. 1H NMR (400 MHz, CDC13): 57.58 (dd, lH), 7_21 (dd, lH), 6.51 (dd, lH), 6.18 (dt, 2H), 6.00 (t, lH), 5.16 (s, 2H) , 3.62 (br, 4H) -33- 201030056 [Chem. 19]

(Synthesis Example 2) Synthesis of furan-2-ylmethyl 3,5-diaminobenzoic acid ester In a 500 mL four-necked flask, 25.3 g of 3,5-dinitrobenzimidyl chloride and furanol were added. lO.OmL and tetrahydrofuran 200mL. Further, 9.7 mL of pyridine was added dropwise, and the mixture was stirred at room temperature for 16 hours. After the completion of the reaction, 5 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated sodium hydrogen carbonate and brine. Anhydrous magnesium sulfate was added to the organic layer to conduct dehydration drying, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was purified by silica gel column chromatography (dichloroacetic acid: ethyl acetate = 3:1) to afford 30.3 g of dinitro compound (yield 95%). The results of 1H-NMR measurement of the obtained solid are shown below. From this result, it was confirmed that the obtained solid was the intended dinitro compound. *H NMR (400 MHz, CDC13): 69.23 (t, lH), 9.17 (d, 2H), 7.49 (dd, lH), 6.57 (dd, lH), 6.43 (dd, lH), 5.44 (s , 2H) [Chem. 20]

201030056 Next, a dinitro compound 30.3 g of platinum/carbon 3.1 g and methanol (400 mL) were placed in a 500 mL four-necked flask, and the mixture was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, the mixture was filtered through Celite, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using isopropyl alcohol / hexane = 1 / 1 to give 1 1.6 g of pale brown solid (yield: 48%). The results of 1H-NMR measurement of this pale brown solid are shown below. From this result, it was confirmed that the obtained pale brown solid was the intended diamine. lH NMR (400 MHz, DMSO-d6): 57.71 (dd, 1 Η) &gt; 6.57 (dd, lH) &gt; 6.48 (dd, 2H), 6.4 1 (d, 2H), 6.01 (t, lH), 5.20 (s, 2H), 5.02 (br, 4H) [Chem. 21] o2n

(Synthesis Example 3) Synthesis of N-(3,5-diaminophenyl)furan-2-carboxamide A 3,5-dinitroaniline 24.lg and pyridine 11.7 mL were added to a 500 mL three-necked flask. 300 mL of tetrahydrofuran was added dropwise to 3.8 mL of 2-furoylmethyl chloride, and the mixture was stirred at room temperature for 18 hours. After the completion of the reaction, 50 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated sodium hydrogen carbonate and brine. Next, anhydrous magnesium sulfate was added to the organic layer to carry out dehydration drying, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized from tetrahydrofuran / hexane = 1/3 to give 31. lg of dinitro compound (yield: 85%). The results of the measurement of 1 H-NMR of the solid -35-201030056 obtained are shown below. From this result, it was confirmed that the obtained solid was the intended dinitro compound. !H NMR (400 MHz, DMSO-d6): 51 1 .1 (s, lH), 9_11 (d, 2H), 8.54 (t, lH), 8_05 (dd, lH), 7_46 (dd'lH) ' 6.78 (dd, 1 Η) [Chem. 22]

Next, 30.9 g of a dinitro compound, 4.2 g of platinum/carbon, 300 g of 1,4-dioxane, and 800 g of tetrahydrofuran were placed in a four-liter four-necked flask under a hydrogen atmosphere. After the completion of the reaction, the mixture was filtered through Celite, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized from isopropyl alcohol to give 21.4 g (yield: 89%) of pale brown solid. The results of 1 Η-NMR measurement of this pale brown solid are shown below. From this, it was confirmed that the obtained pale brown solid was the intended diamine. NMR (400 MHz, DMSO-d6): 59.5 1 (s,lH), 7.78 (dd,lH), 7.28 (dd,lH), 6.65 (dd,lH), 6.23 (d,2H), 5.60 (t, lH), 4.73 (br, 4H) -36- 201030056 [化23] ο2ν Ο

Ν〇2

Η2 R/C 1,4-Dioxane, THF

(Synthesis Example 4) Synthesis of 3,5-diaminobenzylthiophene-2-carboxylate (DABTh) φ In a 500 mL (ml) three-necked flask, 2,5-dinitrobenzyl alcohol 21.5 g, 2 was added. - 12.1 mL of thiophenemethyl chloride and 200 mL of tetrahydrofuran. Further, 9.6 mL of pyridine was added dropwise, and the mixture was stirred at room temperature for 48 hours. After the completion of the reaction, 5 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated sodium hydrogen carbonate and brine. Subsequently, anhydrous magnesium sulfate was added to the organic layer to carry out dehydration drying, and after filtration, the solvent was distilled off using a rotary evaporator. The residue was recrystallized from ethyl acetate and hexane to give 2,7 g of dinitro compound (yield: 82%). The results of 1H-NMR measurement of the obtained solid are indicated by ® . NMR (400 MHz, C DC 13): δ 9.0 3 (t, 1H) » 8.66-8.63 (m, 2H), 7.90 (dd, 1H), 7.66 (dd, 1H), 7.17 (dd, 1H), 5.52 (s, 2H) -37- 201030056 [Chem. 24]

17.5 g, uranium/carbon 4.3 g and tetrahydrofuran 200 g, under an atmosphere of hydrogen. After the completion of the reaction, the mixture was filtered through Celite, and the solvent was distilled off using rotary. The residue was subjected to a pale brown solid (12.9 g (yield: 92%) using tetrahydrofuran and isopropyl alcohol. The results of 1H-NMR measurement of the pale brown solid were as follows. 'Η NMR (400 MHz, CD C13) : δ 7.8 3 (dd, 1H) · 1H) &gt; 7.10 (dd, 1H), 6.19-6.17 (m, 2H) &gt; 6.00 5.16 (s, 2H), 3.61 The (br, 4H)-based compound was stirred in a 48-evaporator crystal to give the product. Thus 7.56 (dd, (t, 1H), [Chem. 25]

2-Carboxylic ester (Synthesis Example 5) Synthesis of 3,5-diaminobenzyl-5-methylfuran (MeDABFr) 201030056 Addition of 5-methyl-2-furancarboxylic acid to a 500 mL four-necked flask 8.5 g and 17 mL of dichloromethane were cooled from room temperature to 〇 ° C. Next, 5.9 mL of ethylene dichloride and 0.5 g of DMF were added, and the mixture was stirred at room temperature for 2 hours. After stirring, 3,5-dinitrobenzyl alcohol I3.4 g and 6 mL of pyridine were added, and the mixture was stirred at room temperature for 16 hours. After the completion of the reaction, 50 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated sodium hydrogen carbonate and brine. Next, anhydrous magnesium sulfate was added to the organic layer to remove water, and the mixture was filtered through celite, and then the solvent was distilled off using a rotary evaporator. The residue was washed with isopropyl alcohol to obtain 17.1 g of a dinitro compound (yield: 6%). The measurement results of 1H NMR of the obtained solid are shown below. *Η NMR (400 MHz, CDC13): 59.02 (t, 1H)- 8.65-8.62 (m, 2H), 7_23-7.21 (m, lH), 6.20-6.18 (m, lH), 5.52-5.50 (m, 2H), 2.43-2.41 (m, 3H) [Chem. 26]

To a 500 mL four-necked flask, 16.7 g of a mononitro compound, 1.7 g of platinum/carbon and 17 g of tetrahydrofuran were added, and the mixture was stirred under a hydrogen atmosphere for 21 hours. After the reaction was completed, the diatomaceous earth was filtered. The solvent was distilled off using a rotary evaporator. Recrystallization of the residue was carried out using isopropyl alcohol to give a pale brown solid 9.1 g (yield 68%). -39- 201030056 The measurement results of 1η-nmr of this pale brown solid are as follows. From this result, it was confirmed that the obtained pale brown solid was the intended diamine. *H NMR (400 MHz, CDC13): 67.15 (d, 2H) &gt; 7.10 (d, 1H), 6.11-6.09 (m, 1H), 5.97 (t, 1H), 5.13 (s, 2H), 3.57 ( Br, 4H) &gt; 2.37 (s, 3H) [27]

(Synthesis Example 6) Synthesis of 3,5-diaminobenzylfuran-3-carboxylate (3-DABFr) To a 500 mL four-necked flask, 8.2 g of 3-furancarboxylic acid and 240 mL of dichloromethane were added. Cool to 〇 ° C at room temperature. Next, 6.4 mL of ethylene dichloride and 0.5 g of DMF were added, and the mixture was stirred at room temperature for 2 hours. After stirring, 15 g of 3,5-dinitrobenzyl alcohol and 9.7 mL of pyridine were added, and the mixture was stirred at room temperature for 47 hours. After the completion of the reaction, 50 mL of pure water was added and stirred for 1 hour. The organic layer was extracted with ethyl acetate, and the organic layer was washed with 1N hydrochloric acid, saturated sodium hydrogen carbonate and brine. Next, anhydrous magnesium sulfate was added to the organic layer to carry out dehydration and drying, and after filtration, the solvent was distilled off using a rotary evaporator. Recrystallization of the residue using ethyl acetate gave 16.8 g of a dinitro compound (yield 78%). The measurement results of 1 η N M R of the obtained solid are shown below. *Η NMR (400 MHz, CD C13) : δ 9.0 3 (t, 1H) &gt; 8.63-8.61 201030056 (m, 2H), 8.12 (dd, 1H), 7.4 1 (dd, 1H), 6.79 (dd, 1H), 5.48(d, 2H) [28]

To a 500 mL four-necked flask, 16.5 g of a dinitro compound, 1.7 g of platinum/carbon, and 165 g of tetrahydrofuran were added, and the mixture was stirred under a hydrogen atmosphere for 29 hours. After the reaction was completed, the diatomaceous earth was filtered. The solvent was distilled off using a rotary evaporator. Recrystallization of the residue using tetrahydrofuran and isopropanol gave 7.4 g (yield: 57%) of pale brown solid. The measurement results of 1 Η - N M R of this pale brown solid are as follows. From this result, it was confirmed that the obtained pale brown solid was the intended diamine. Φ *H NMR (400 MHz, CDC13): 58.04 (dd, 1H) » 7.42 (dd, 1H), 6.77 (dd, 1H), 6.14 (d, 2H), 5.98 (t, 1H), 5.10 (s, 2H), 3.57 (br, 4H) [Chem. 29]

-41 - 201030056 The abbreviations of the compounds used in the synthesis of polyaminic acid and polyimine are as follows. &lt;tetracarboxylic dianhydride&gt; CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic dianhydride &lt;diamine&gt; 2- DABFr: 3,5-diaminobenzylfuran-2-carboxylate FrDAB: furan-2-ylmethyl 3,5-diaminobenzoate DAAFr: N-(3,5-diaminophenyl)furan-2-carboxamide DABTh: 3,5-diaminobenzylthiophene-2-carboxylate MeDABFr: 3,5-diaminobenzyl 5--5-methylfuran-2-carboxylate 3- DABFr3,5-diaminobenzylfuran-3-carboxylate Me4APhA: 4-amino-N-methylphenethylamine p-PDA: p -phenylenediamine DDM: 4,4'-diaminodiphenylmethane C14DAB: 4-tetradecyl-1,3-diaminobenzene C16DAB: 4-hexadecyl-1,3-diamine Benzene 3-ABA: 3-aminobenzylamine &lt;organic solvent&gt; NMP: N-methyl-2·pyrrolidone γ-ΒΙ^: γ-butyrolactone BC: butyl-cellosolve DPM: dipropylene glycol monomethyl ether 201030056 DMF: dimethylformamide &lt;Measurement of molecular weight&gt; The molecular weight of polylysine or polyimine obtained by polymerization is by GPC (normal temperature gel permeation chromatography) device, and polyethylene The diol and polyethylene oxides are converted to 値, and the number average molecular weight is calculated. An average molecular weight. _ GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: Shodex pipe column (inline of KD-803, KD-805)

Column temperature: 50 °C Dissolution: N,N'-dimethylformamide (additive lithium bromide-hydrate (LiBr*H20) is 30mmol/L, pity acid. Anhydrous crystal (〇-pity) It is 30 mmol/L, tetrahydrofuran (THF) is l〇ml/L) Flow rate: 1.0 ml/min Calibration curve Preparation Standard sample: TSK standard polystyrene ethylene oxide manufactured by Tosoh Corporation (molecular weight: about 900,000, 150,000, 100,000, 3 0,000) and polymer polyethylene glycol manufactured by LABORATORY Co., Ltd. (molecular weight: about 12,000, 4,000, 1,000) 〇 &lt;Measurement of sulfhydrylation rate&gt; 醯imination rate of polyimine obtained by chemical imidization The polyimine was dissolved in d6-DMSO (dimethyl sulfonium-d6), and W-NMR was measured. The ratio of the peaks of proton peaks was calculated to obtain the proline group remaining without imidization. ratio. -43-201030056 &lt;Production of liquid crystal cell&gt; The liquid crystal cell was produced in the following manner by the liquid crystal alignment treatment agent prepared in the examples and the comparative examples. The liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C for 70 seconds, and then fired on a hot plate at 210 ° C for 1 minute to form a film thickness. 〇〇nm coating film. The surface of the coating film was rubbed with a rayon cloth at a roller diameter of 120 mm using a rayon cloth at a number of revolutions of 100 rpm, a roller _ travel speed of 50 mm/sec, and a pushing amount of 3.3 mm to obtain a liquid crystal alignment. The substrate of the film. Preparing two substrates with a liquid crystal alignment film, wherein one of the liquid crystal alignment films is spread on the surface of the film, and then the sealant is printed on the upper surface, so that the other substrate is opposed to the liquid crystal alignment film surface, and the rubbing direction is orthogonal. After the state is applied, the sealant is hardened to form an empty unit cell. This empty cell was injected into a liquid crystal MLC-2003 (manufactured by Merck) by a pressure reduction injection method, and the injection port was closed to obtain a twisted nematic liquid crystal cell.方法 The method for measuring the physical properties and the property evaluation of each liquid crystal cell after production is as follows. Tables 2 and 3 show the results of the composition of each of the liquid crystal alignment treatment agents, the physical property measurement and the characteristic evaluation of each of the liquid crystal alignment films in Examples 1 to 9 and Comparative Examples 1 to 3. &lt;Evaluation of Friction Resistance&gt; A substrate having a liquid crystal-44 - 201030056 film was produced by the method described in the above &lt;Production of Liquid Crystal Cell&gt;. At this time, the amount of the friction condition was changed to 〇.5 mm. The surface of the obtained liquid crystal alignment film was observed by a confocal laser microscope, and the following evaluation was carried out. 〇: No cut slag or friction damage was observed. △: Cut slag or friction damage was observed. X: The film was peeled off or the frictional damage was visually observed. Φ <Liquid alignment evaluation> In order to distinguish the advantages and disadvantages of the liquid crystal alignment, the following liquid crystal cells were produced. The liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70° C. for 70 seconds, and then fired on a hot plate at 210° C. for 10 minutes to form a film thickness of 100 nm. Coating film. The surface of the coating film was rubbed with a rayon cloth at a roller rotation speed of 10 mm rpm, a roller traveling speed of 50 mm/SeC, and a pushing amount of 0.2 mm to obtain a substrate with a liquid crystal alignment film. . Two substrates with a liquid crystal alignment film are prepared, and a spacer of 6 μm is dispersed on one liquid crystal alignment film surface, and then a sealant is printed thereon to cause the other substrate to face in the liquid crystal alignment film surface, rubbing direction After bonding to a state of 180 °, the sealant is cured to form an empty cell. This empty cell was injected into a liquid crystal MLC-2 00 3 (manufactured by MerCk) by a pressure reduction injection method, and the injection port was closed to obtain an antiparallel liquid crystal cell. The initial alignment of the liquid crystal cell was visually observed. As evaluated below. The results are shown in Table 2 to be described later. 〇: Good alignment. X: A lot of light leakage or poor alignment was observed. -45-201030056 &lt;Pretilt angle measurement&gt; The twisted nematic liquid crystal cell produced by the method described in the above &lt;Production of liquid crystal cell&gt; was heated at 105 ° C for 5 minutes, and then the pretilt angle and voltage holding ratio were measured. . The pretilt angle was measured using a crystal rotation method. &lt;Measurement of Voltage Retention Rate&gt; The measurement of the voltage holding ratio of the twisted nematic liquid crystal cell produced by the method described in the above &lt;Production of Liquid Crystal Cell&gt; is at a temperature of 90 ° C, at 60 ° C A voltage of 4 V was applied, and the voltage after 16.67 ms was measured, and how much the voltage was maintained, which was calculated as the voltage holding ratio. The voltage holding ratio was measured by using a VHR-1 voltage holding ratio measuring device manufactured by Dongyang Technic Co., Ltd. &lt;Evaluation of Accumulated Charge (RDC)&gt; The twisted nematic liquid crystal cell produced by the method described in the above &lt;Production of Liquid Crystal Cell&gt; is separated by 〇V to 0.1 V at a temperature of 23 °C. A DC voltage was applied to 1.0 V, and the flicker amplitude level of each voltage was measured to prepare a calibration curve. After 5 minutes indirectly, an alternating voltage of 3.0 V and a direct current voltage of 5.0 V were applied, and after one hour, the flicker amplitude level after only the direct current voltage was 〇V was measured, and the RDC was estimated by comparison with a calibration curve prepared in advance. (This RDC estimation method is called scintillation reference method) -46 - 201030056 (Example 1) The tetracarboxylic dianhydride component is CBDA 5.00 g (0.025 mol), and the diamine component is 2-DABFr 6.03 g (0.026). Mol) 'In NMP 44.14g, the reaction was carried out for 16 hours at room temperature to obtain a solution having a polyamine acid (PA A-1) concentration of 20% by mass. The polyperuric acid (PAA-1) solution was diluted with NMP 23.3 g and BC 10·Og to obtain a liquid crystal alignment treatment agent having a polyamine acid (PAA-1) of 4.6% by mass. Using this liquid crystal alignment agent, φ was evaluated for friction resistance, pretilt angle, voltage holding ratio (VHR), and RDC. The results are shown in Table 2. (Example 2) In a polyacrylic acid (PAA-1) solution (PAA-1 concentration: 20% by mass) 408 obtained in the same manner as in Example 1, NMP 9 3.3 3 3 was added, followed by addition of acetic anhydride 5.7 7 . g and pyridine 2 · 3 9 g were reacted at 40 ° C for 3 hours to carry out hydrazine imidization. After the reaction solution was cooled to room temperature, it was poured into 500 ml of methanol to recover a precipitated solid. Further, the solid matter was washed twice with methanol, and then dried under reduced pressure at 100 ° C to obtain a white powder of polyethylenimine (SPI-1). The polyimine had a number average molecular weight of 13,2,04 and a weight average molecular weight of 30,700. The sulfhydrylation rate was 87%. 18.0 g of γ-BL was added to 2.00 g of the obtained polyimine (SPI-1), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, 8.0 g of γ-BL, 6.00 g of BC, and 6.00 g of DPM were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a liquid crystal alignment treatment agent having a polyamidolimine (SPI-1) of 5% by mass. The liquid crystal alignment treatment agent was used in the same manner as in Example 1 -47-201030056. The results are shown in Table 2. (Example 3) The tetracarboxylic dianhydride component was obtained by using CBD A 5.52 g (〇. 02 8 mol), and the diamine component was 2-DABFr 2.00 g (0.009 mol) and 3-ABA l_40 g (0.01 1 mol). And C14DAB 2 · 7 6 g (0 · 0 0 9 m ο 1), reacted in NMP 46.7g at room temperature for 16 hours to obtain a solution of polyamine acid (PA A-2) at a concentration of 2 〇 mass % . This poly-proline (PAA-2) solution was diluted with NMP 23.3 g and BClO.Og to obtain a liquid crystal alignment treatment agent having a polyamic acid (P A A-2) of 4.6 mass%. This liquid crystal alignment treatment agent was evaluated in the same manner as in Example 1. The results are shown in Table 2. (Example 4) In a polyacrylic acid (PA A-2) solution (PA A-2 concentration: 20% by mass) 4 0.08 obtained in the same manner as in Example 3, a dilution of \1^?93.38 was added, and then B was added. 6.02 g of an acid anhydride and 2.49 g of pyridine were reacted at 60 ° C for 3 hours to carry out hydrazylation. After the reaction solution was cooled to room temperature, it was poured into 500 ml of methanol to recover a precipitated solid. Further, the solid matter was washed twice with methanol, and then dried under reduced pressure at 10 ° C to obtain a white powder of polyethylenimine (SPI-2). The polyimine had a number average molecular weight of 15,850 and a weight average molecular weight of 42,234. The sulfhydrylation rate was 92%. 18.0 g of γ-BL was added to 2.00 g of this polyimine (SPI-2), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8_00 g, BC 6.00 g, and DPM 6.00 g were added to the solution, and the mixture was stirred at -48 - 201030056 50t for 20 hours to obtain a liquid crystal alignment treatment agent having a polyamidolimine (SPI-2) of 5% by mass. This liquid crystal alignment treatment agent was evaluated in the same manner as in Example 1. The results are shown in Table 2. (Example 5) The tetracarboxylic dianhydride component was 5.57 g (0,029 mol) using CBDA, and the diamine component was 2.0 g (0.009 mol) of FrDAB, 1.42 g (0.012 mol) of 3-ABA, and 2.79 g (0.009) of C14DAB. Mol) was reacted at room temperature for 16 hours in NMP 46.7 g to obtain a solution having a polyamine acid (PAA-3) concentration of 20% by mass. The polyacrylic acid (PAA-3) solution was diluted with NMP 23.3 g and BClO.Og to obtain a solution of polyamine acid (PAA-3) of 4.6% by mass to obtain a liquid crystal alignment treatment agent of the present invention. . The coating liquid was used and evaluated in the same manner as in Example 1. The results are shown in Table 2. φ (Example 6) In a 40.Og solution of a polyacrylic acid (PAA-3) solution (PAA-3 concentration: 20% by mass) obtained in the same manner as in Example 5, 93.3 g of NMP was added and diluted, and then acetic anhydride 6_06 g was further added. The ruthenium imidization was carried out by reacting with pyridine 2.53 g at 60 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was poured into methanol (500 ml), and the precipitated solid was collected. Further, this solid matter was washed twice with methanol, and then dried under reduced pressure at 10 ° C to obtain a white tan powder of polyimine (SPI-3). The polyimine had a number average molecular weight of 17,920 and a weight average molecular weight of 41,290. The hydrazine imidation rate was 89%. -49- 201030056 18.0 g of γ-BL was added to 2.00 g of this polyimine (SPI-3), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.00 g, BC 6.00 g, and DPM 6.00 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a liquid crystal alignment treatment agent of 5 mass % of polyimine (SPI-3). This liquid crystal alignment treatment agent was evaluated in the same manner as in Example 1. The results are shown in Table 2. (Example 7) The tetracarboxylic dianhydride component was 5.57 g (〇.〇29 mol) of CBDA, and DAAFr l_89g (0.009 mol), 3-ABA 1.42 g (0.012 mol), and C14DAB 2.79 g of the diamine component. 0.009 mol), reacted at room temperature for 16 hours in NMP 46.7 g to obtain a solution of polyamine acid (PAA-4) at a concentration of 2% by mass. The polyaminic acid (PAA-4) solution was diluted with NMP 23.3 g and BClO.Og to obtain a solution of polyamine acid (PA A-4) of 4.6% by mass to obtain a liquid crystal of the present invention. Orientation treatment agent. This coating liquid was used in the same manner as in Example 1. The results are shown in Table 2. (Example 8) A polylysine (PAA-4) solution (PAA-4 concentration: 20% by mass) obtained in the same manner as in Example 7 was used. (In addition, NMP 93.3 g was added and diluted, and then acetic anhydride 6 was further added. 0 6 g and pyridine 2 · 5 3 g were reacted at 60 ° C for 3 hours to carry out hydrazine imidization. The reaction solution was cooled to room temperature, and then poured into methanol (500 ml) to recover a precipitated solid. The solid matter was washed twice with methanol, and dried under reduced pressure at 100 Torr to obtain a white tea 201030056 color powder of polyimine (SPI-4). The number average molecular weight of the polyimine was 15,367, and the weight average molecular weight was 39,880. The yield of ruthenium was 90%. 18.0 g of γ-BL was added to 2.00 g of this polyimine (SPI-4), and the mixture was stirred at 50 ° C for 20 hours. At the end of the stirring, the polyimine was completely dissolved. Further, γ-BL 8.00 g, BC 6.00 g, and DPM 6.00 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a liquid crystal alignment treatment agent having a polyamidimide (SPI-4) of 5% by mass. The liquid crystal alignment treatment agent was evaluated in the same manner as in Example 1. The results are shown in Table 2. (Example 9) The tetracarboxylic dianhydride component was TDA 12.0 g (0.040 m〇l). The diamine component was 2.59 g (0.024 mol) of P-PDA, 2.79 g (0.012 mol) of 2-DABFr, and 1.39 g (0.004 mol) of C 16 6DAB, and reacted at 5 ° C in NMP 75.7 g. In an hour, a solution having a concentration of polyamic acid of 20% by mass is obtained. Φ 90.0 g of this polyaminic acid solution is diluted with 187 g of NMP, and then added with acetic anhydride 3 9 · 6 g and pyridine 1 8.4 g at 40 ° C After reacting for 3 hours, the reaction solution was cooled to room temperature, and then poured into 1.17 L of methanol to recover the precipitated solid matter. The solid matter was washed twice with methanol, and then washed. The white powder of polyimine (SPI-5) was obtained by drying under reduced pressure at ° C. The number average molecular weight of this polyimine was 15,322, and the weight average molecular weight was 28,239. The oxime imidization ratio was 81%.

To the 5.00 g of this polyimine (SPI-5), 62.5 g of γ-BL was added, and the mixture was stirred at 50 ° C -51 - 201030056 for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 2 〇.8 g was added to the solution, and the mixture was stirred at 5 ° C for 20 hours to obtain a solution of 5.7% by mass of polyimine (SPI-5). In addition, CBDA 9.80g (0.050mol), PMDA 9.60g (0.0 4 4 m ο 1), DD Μ 1 9 · 8 g (0 · 1 0 m ο 1), in Ν Μ P 1 1 1 g and γ In a mixed solvent of -BLlllg, the solution was reacted at room temperature for 5 hours to prepare a solution having a concentration of polyamine acid (PAA-5) of 15% by mass. The polyamido acid coefficient had an average molecular weight of 10,925 and a weight average molecular weight of 27,314. To 200 g of this polyaminic acid (PAA-5) solution, 225 g of γ-BL and 75.0 g of BC were added, and the mixture was stirred at room temperature for 2 hours to obtain a solution of polyamine acid (PAA-5) of 6 mass%. 200 g of a 6 mass% solution of the polyamic acid (PAA-5) and 50.0 g of a 6 mass% solution of the polyimine (SPI-5) obtained above were stirred at room temperature for 20 hours, and then solid content (PAA) The total mass concentration of -5 and SPI-5 was adjusted to 5.9% by mass to obtain a liquid crystal alignment treatment agent (BL-1) of the present invention. This liquid crystal alignment treatment agent was used in the same manner as in Example 1. The results are shown in Table 2. (Example 10) The tetracarboxylic dianhydride component was CBDA 5.7 8 g (0.029 mol) 'diamine component using DABTh 2.24 g (0.009 mol), 3-AB A 1.47 g (0.012 mol), and C14DAB 2 · 8 9 g (0.0 0 9 m ο 1), in NMP 44.96g, reacted at room temperature for 16 hours to obtain 20% by mass of poly-proline solution (PAA-6). Poly-proline solution (PAA-6) 10.0 g was diluted with NMP 23.3 g and 201030056 BC 10.0 g to form a solution having a solid content of 4.6 mass%, and the liquid crystal alignment treatment agent of the present invention was obtained. This coating liquid was used in the same manner as in Example 1. The results are shown in Table 2. (Example 1 1) In a 40 g of polyacrylic acid (PAA-6) solution (PAA-6 concentration: 20% by mass) obtained in the same manner as in Example 10, 'addition of NMP 93.33 g of dilution' ❿ followed by addition of acetic anhydride 5.61 g The ruthenium imidization was carried out by reacting with pyridine 2.32 g ' at 60 ° C for 3 hours. The reaction solution was cooled to room temperature and then poured into 500 ml of methanol to recover the precipitated solid. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at 1 ° C to obtain a white powder of polyethylenimine (SP 1-6). The polyimine had a number average molecular weight of 13,163' weight and an average molecular weight of 30,211. The hydrazine imidation rate was 85%. To the 2.00 g of this polyimine (SPI-7), γ-BL 18.0 g' was added and stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.00 g, and DPM 6.00 g were added to the solution of φ, and the mixture was stirred at 50° C. for 20 hours to obtain a solution of 5 mass % of polyimine (SPI-6) to obtain the present invention. Liquid crystal alignment treatment agent. This coating liquid was used in the same manner as in Example 1. The results are shown in Table 2. (Example 12) The tetracarboxylic dianhydride component was 5.57 g (0.029 mol) using CBDA, and the e amine component was M eD AB F r 2.1 4 g (0 · 0 9 mo 1), 3 - ABA 1 · 4 2 g (0.012 mol), and C14DAB 2.7 9 g (0.0 0 9m o 1) &gt; In NMP46.7g -53- 201030056, reacted at room temperature for 16 hours to obtain the concentration of poly-proline (pa A-7) 20% by mass solution. The polyaminic acid (PAA-7) solution was diluted with NMP 23.3 g and BClO.Og to form a solution of polyamine acid (PAA-7) of 4.6% by mass to obtain the liquid crystal alignment of the present invention. Treatment agent. The same evaluation as in Example 1 was carried out using this coating liquid. The results are shown in Table 2. (Example 13) A polyacrylic acid (PAA-7) solution (PAA-7 concentration: 20% by mass) 4 obtained in the same manner as in Example 1 was added, and NMP 93.3 g was added thereto, followed by addition of acetic anhydride 6.0. 6 g and pyridine 2 · 5 3 g were reacted at 60 ° C for 3 hours to carry out hydrazine imidization. After cooling the reaction solution to room temperature, it was poured into 500 ml of methanol to recover the precipitated solid matter. The solid matter was washed twice with methanol, and then dried under reduced pressure at 100 ° C to obtain a white tan powder of polyimine (SPI-7). The number average molecular weight of the polyimine was 15.787 and the weight average molecular weight was 3.43. 3. The imidization ratio of ruthenium was 87%. 18.0 g of γ-BL was added to 2.00 g of this polyimine (SPI-7), and stirred at 5 ° C for 20 hours. At the end of the stirring, the polyimine was completely dissolved. Further, γ-BL 8.00 g, BC 6.00 g, and DPM 6.00 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a solution of 5 % by mass of polyimine (SPI-7), thereby obtaining the present invention. The liquid crystal alignment treatment agent was used in the same manner as in Example 1. The results are shown in Table 2. (Example 14) 201030056 The tetracarboxylic dianhydride component was CBDA. 5.57g (0.029mol), diamine component using 3-DABFr 2.02g (0.009mol) ' 3-ABA 1.42g (0.012mol), and C14DAB 2 · 7 9 g (0.0 0 9 m ο 1), in NMP46. In 7 g, the reaction was carried out at room temperature for 16 hours to obtain a solution of polyamine acid (PAA-8) at a concentration of 20% by mass. The polyamine acid (PAA-8) solution was 10.3 g using NMP 23.3 g and BClO. The Og was diluted to form a solution of polyamine acid (PAA-8) of 4.6% by mass, and φ was obtained to obtain a liquid crystal alignment treatment agent of the present invention. The same evaluation as in Example 1 was carried out using the coating liquid. (Example 15) A polylysine (PAA-8) solution (PAA-8 concentration: 20% by mass) obtained in the same manner as in Example 14 was used. (In addition, NMP 93.3 g was added and diluted, and then acetic anhydride was further added. 6.06 g and 2.53 g of pyridine were reacted at 60 ° C for 3 hours to carry out hydrazine imidization. After cooling the reaction solution to room temperature, it was poured into 500 ml of methanol to recover the precipitated solid matter. After washing with methanol twice, it was dried under reduced pressure at 100 ° C to obtain a white tan powder of polyimine (SPI-8) having a number average molecular weight of 16,142 and a weight average molecular weight. 8,5 3 74 »acyl imidization was 89%. This polyimide (SPI-8) in the γ-BL 18.0g was added 2.00g, stirred at 50 ° C 20 h. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.00 g, BC 6_00 g, and DPM 6.00 g were added to the solution, and 5 (TC was stirred for 20 hours to obtain a liquid crystal alignment treatment agent having a polyamidimide (SPI-8) of 5% by mass. The alignment treatment agent was evaluated in the same manner as in Example 1 at -55-201030056. The results are shown in Table 2. The tetracarboxylic dianhydride component was 5.57 g (0.02 9 mol) using CBDA, and 2-DABFr 2.02 g (0.009 mol) was used as the diamine component. And Me4APhA 3.05g (0.021mol), and reacted at room temperature for 16 hours in NMP46.7g to obtain a solution of polyglycine (PAA-9) at a concentration of 20% by mass. The molecular weight is 2 1,329, and the weight average molecular weight is 45, 2 94. The polyamine acid (PAA-9) solution of 10.Og is diluted with NMP 23.3g and BC 10 .Og to form poly-proline (PAA-9). The liquid crystal alignment treatment agent of the present invention was obtained in a solution of 4.6% by mass. The same evaluation as in Example 1 was carried out using the coating liquid. The results are shown in Table 2. (Comparative Example 1) The tetracarboxylic dianhydride component was Using CBDA 12.5g (0_064mol), the diamine component used 3-ABA 5.56g (0_046mol), and C14DAB 6.25g (0.020mol), in NMP97.20g, at room temperature After 16 hours, a solution of 20% by mass of polyglycine (PAA-10) was obtained. The solution of polylysine (PAA-10) was diluted with NMP 23.3 g and BClO.Og to form a poly A solution having a concentration of lysine (PAA-10) of 4.6% by mass was obtained, and a liquid crystal alignment treatment agent to be compared was obtained. Using this coating liquid, liquid crystal cells were produced in the same manner as in Example 1, and physical properties were measured and evaluated. (Comparative Example 2) In 50 g of polyacrylic acid (PAA-10) solution-56-201030056 (PAA-10 concentration: 20% by mass) obtained in the same manner as in Comparative Example 1, 116.67 g of NMP was added and diluted, and then acetic anhydride was added. 7.39 g and 3.15 g of pyridine were reacted at 70 ° C for 3 hours to carry out hydrazine imidation, but gelation occurred in the reaction. Again, the polylysine (PAA-10) solution obtained in the same manner as in Comparative Example 1 ( In 50 g of PAA-10 concentration, 50 g of NMP was added and diluted with 116.67 g of NMP, and then 7.37 g of acetic anhydride and 3.15 g of pyridine were added, and hydrazylation was carried out at a reaction temperature of 50 ° C. φ The reaction solution was cooled to After being at room temperature, it is poured into 250 ml of methanol to recover the precipitated solid matter. After washing with methanol twice, it was dried under reduced pressure at 100 Torr to give a white powder of polyethylenimine (SPI-9). The polyimine had a number average molecular weight of 1,6,33.8 and a weight average molecular weight of 39,865. The hydrazine imidation rate is 80%. To the poly-imine (SPI-9) lg, 9 g of γ-BL was added, and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 4.0 g, BC 3.0 g, and DPM 3.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a solution of 5 mass % of polyimine (SPI-9), which was obtained as a comparison object. Liquid crystal alignment treatment agent. Using the liquid crystal alignment agent, liquid crystal cells were produced in the same manner as in Example 1, and physical properties were measured and evaluated. (Comparative Example 3) The tetracarboxylic dianhydride component was 5.70 g (0.029 mol) using CBDA, and Me4APhA 4 · 5 1 g (0 · 0 3 0 m ο 1 ) was used as the diamine component in N MP 4 6.7 g The reaction was carried out at room temperature for 16 hours to obtain a solution of polyglycine (PAA-1 1) at a concentration of 20 mass - 57 - 201030056 %. The polyammonic acid had a number average molecular weight of 1,9,630 and a weight 2P average molecular weight of 48,201. The polyamine acid (PAA-11) solution was diluted with NMP 23.3 g and BC 10 ·Og to form a solution of polyamine acid (PAA-11) of 4.6% by mass, and the liquid crystal alignment was obtained as a comparison object. Treatment agent. A liquid crystal cell was produced in the same manner as in Example 1 using this liquid crystal alignment treatment agent, and physical properties were measured and properties were evaluated.

-58- 201030056 [Table 1]

Polyamide or polyamidiamine oxime iodization rate [%] acid dianhydride diamine component PAA-1 — CBDA (0.025) 2-DABFr (0.026) PAA-2 — CBDA (0.028) 3-ABA (0.011 ), 2-DABFr (0. 009), C14DAB (0. 009) PAA-3 — CBDA (0.029) 3-ABA(0.012), FrDAB(0.009), C14DAB (0. 009) PAA-4 — CBDA (0.029 ) 3-ABA (0.012), DAAFr (0.009), C14DAB (0. 009) PAA-5 — CBDA (0.050) PMDA (0.044) DDM (0. 10) PAA-6 — CBDA (0.029) 3-ABA (0.012 ), DABTh(0.009), C14DAB (0. 009) PAA-7 — CBDA (0.029) 3-ABA(0.012), MeDABFr(0. 009), C14DAB (0. 009) PAA-8 — CBDA (0. 029 ) 3-ABA (0. 012), 3-DABFr (0. 009), C14DAB (0. 009) PAA-9 — CBDA (0.029) Me4APhA (〇. 021), 2-DABFr (0. 009) PAA- 10 — CBDA (0. 064) 3-ABA(0. 046), C14DAB (0. 020) PAA-11 — CBDA (0.029) Me4APhA (0.030) SPI-1 87 CBDA (0.025) 2-DABFr (0. 026 SP1-2 92 CBDA (0.028) 3-ABA (0.011), 2-DABFr (0. 009), C14DAB (0. 009) SPI-3 89 CBDA (0. 029) 3-ABA (0. 012), FrDAB (0.009), C14DAB (0. 009) SPI-4 90 CBDA (0.029) 3-ABA(0.012), DAAFr (0.009), C14DAB (0. 009) SPI-5 8 1 TDA(0. 040) p-PDA (0. 024), 2-DABFr (0.012). Cl 6DAB (0. 004) SPI-6 85 CBDA (0.029) 3-ABA (0.012), DABTh (0.009), C14DAB (0.009) SPI-7 87 CBDA (0.029) 3-ABA (0. 012), MeDABFr (〇. 009), C14DAB (0. 009) SPI-8 89 CBDA (0.029) 3-ABA (0. 012) , 3-DABFr (0. 009), C14DAB (0. 009) SPI-9 80 CBDA (0.064) 3-ABA (0. 046), C14DAB (0. 020) -59- 201030056 [Table 2] Polyamide Acid or polyimine [mass ratio] Liquid crystal alignment frictional resistance tilt angle 0 Voltage retention ratio (%) RDC m Example 1 ΡΑΑ-1 〇〇1.0 93 0.26 Example 2 SPI-1 〇〇1.2 95 0.22 Example 3 ΡΑΑ-2 〇〇6.2 94 0.20 Example 4 SPI-2 〇〇4.1 96 0.11 Example 5 ΡΑΑ-3 〇〇4.8 92 0.22 Example ό SPI-3 〇〇3.8 94 0.12 Example 7 ΡΑΑ-4 〇〇 5.5 94 0.19 Example 8 SPI-4 〇〇4.1 96 0.10 Example 9 PAA-5/SPI-5(8/2) 〇〇3.1 92 0.18 Example 10 PAA-6 〇〇6.0 93 0.20 Example 11 SPI- 6 〇〇 4.3 94 0.15 Example 12 PAA-7 〇〇 6.2 92 0.22 Example 13 SPI-7 〇〇 4.1 95 0.13 Example 14 PAA-8 〇〇6.1 93 0.20 Example 15 SPI-8 〇〇4.0 94 0.12 Example 16 PAA-9 〇〇1.0 96 0.25 Comparative Example 1 PAA-10 〇Δ 4.5 87 0.50 Comparative Example 2 SPI-9 〇X 3.1 92 0.45 Comparative Example 3 PAA-11 〇X 1.2 92 0.88 [Industrial Applicability] With the liquid crystal alignment treatment agent of the present invention, film peeling or cutting resistance during rubbing can be obtained, and the voltage holding ratio is high, and even When a DC voltage is applied to the liquid crystal cell, the liquid crystal alignment agent of the liquid crystal alignment film in which the initial charge is accumulated is less likely to occur. Therefore, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention can be a highly reliable liquid crystal display device, and non-60-201030056 is often applied to a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, and a VA. A display element produced in various ways, such as a liquid crystal display element, an IPS liquid crystal display element, an OCB liquid crystal display element, or the like. The entire contents of the specification, the scope of the patent application and the summary of the disclosure of the patent application No.

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Claims (1)

201030056 VII. Patent application garden 1. A liquid crystal alignment treatment agent characterized in that it comprises a polyamine acid obtained by reacting a diamine component containing a diamine of the following formula [1] with a tetracarboxylic dianhydride component. And a polymer of at least one of a group of polyimine obtained by subjecting the polyamic acid to ruthenium imidation, [Chem. 1] h2n, nh2 (wherein X represents a single bond, an alkylene group having a carbon number of 1 to 3, -OCH2-'-CH20C0-, -NHCO-, -CONH-, or -COOCH2-, and Y represents an oxygen atom or a sulfur atom. Any hydrogen atom of the five-membered ring may be substituted by an alkyl group having 1 to 5 carbon atoms). 2. The liquid crystal alignment treatment agent of claim 1, wherein γ of the formula 为 is an oxygen atom. 3. The liquid crystal alignment treatment agent of claim 1, wherein γ of the formula [1] is a sulfur atom. 4. The liquid crystal alignment treatment agent according to any one of claims 1 to 3 wherein X of the formula [1] is -CH2OCO-, -NHCO-, or · cooch2-. 5. The liquid crystal alignment treatment agent of claim 1, wherein X is -CH2〇CO-, -NHCO-, or -COOCH2-, Y is an oxygen atom. 6. Liquid crystal alignment as claimed in any one of claims 1 to 5 - 62 - 201030056 Physical agent ' Any hydrogen atom of the five-membered ring of the formula [1] is substituted with a methyl group. 7. A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 6. A liquid crystal display element is characterized in that it has the liquid crystal alignment film of claim 7 of the patent application. A diamine characterized by the following formula [2], [Chemical 2] (Any hydrogen atom of the furan ring may be substituted by an alkyl group having 1 to 5 carbon atoms). 10. The diamine of claim 9, wherein any of the hydrogen atoms of the furan ring may be substituted by a methyl group. A polyimine which is characterized in that the polyamine contained in a diamine component containing a diamine of the claim φ 9 or 10 and a tetracarboxylic dianhydride component are obtained, or the polyamine The acid is obtained by hydrazine imidization. 201030056 IV. Designated representative map: (1) The designated representative figure of this case is: None (2), the symbol of the representative figure is simple: no 201030056 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4 -