TW201219450A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents

Abstract

A liquid crystal aligning agent is characterised in having at least one polymer selected from a group comprising: polyamic acids obtained by reacting a diamine component containing a diamine compound represented by formula [1] with a tetracarboxylic acid dianhydride; and polyimides obtained by the imidization of said polyamic acids. (In the formula, X1 represents a single bond, -CH2O-, -O-, -COO-, -OCO-, -NHCO-, or -CONH-, X2 represents a C1-3 alkylene group, X3 represents -O-, -NH-, or -N(R1)-, X4 represents a single bond, -O-, -S-, or -NH-. X5 represents a single bond or a carbon ring selected from the group [X5-1] - [X5-5], X6 represents a C1-18 straight-chain or branched alkyl group, X7 represents a hydrogen atom, -R2-, -OR3, -NHR4, -N(R5)2, or -SR6. Here, R1-R6 each independently represent a C1-5 alkyl group. n represents an integer of 1 or 2.) (In the carbon ring structure, an arbitrary hydrogen atom can be substituted by CH3.)

Description

201219450 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel diamine compound which is useful as a raw material of a polymer used for a liquid crystal alignment film, and a polyamic acid and a polyamidene obtained therefrom. An amine, and a liquid crystal alignment treatment agent. Further, there is a liquid crystal display element having a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent. More specifically, a liquid crystal alignment treatment agent for a liquid crystal alignment film for vertical alignment, a liquid crystal alignment film and a method for forming the same, and a liquid crystal display having such a liquid crystal alignment film can be formed by a small amount of polarized or non-polarized radiation. Component and optical characteristic member. [Prior Art] The liquid crystal alignment film is a constituent member of a liquid crystal display element which is widely used as a display device, and functions as a so-called alignment of liquid crystal in a certain direction. Nowadays, the main liquid crystal alignment film used in the industry is a solution of polylysine (also known as polyglycolic acid), polyamidomate or polyimine from polyimine precursors. The resulting liquid crystal alignment treatment agent is formed. In general, after the liquid crystal alignment treatment agent is applied onto a substrate and heated and calcined, an alignment treatment for making the liquid crystal parallel or obliquely aligned with respect to the substrate surface is performed. In the aspect of the alignment treatment, it is known that the surface of the organic film is rubbed by a cloth such as cotton, nylon or enamel, that is, a surface treatment method called rubbing, a method of vapor-depositing cerium oxide on the surface of a substrate, and using Langmuir - Brochette method (LB method) A method of forming a monomolecular film having a long-chain alkyl group on the surface of a substrate. Among these, particularly in terms of the substrate size -5 - 201219450 t*., the alignment uniformity of the liquid crystal, the processing time, the cost, and the like, it is common to impart liquid crystal alignment by the rubbing treatment. However, in the aspect of imparting the alignment property to the liquid crystal by the rubbing treatment, there is a defect of the liquid crystal alignment film due to the friction, a display defect due to the defect of the liquid crystal alignment film, generation of dust, and occurrence of static electricity due to the occurrence of static electricity. (Thin Film Transistor) Problems such as component loop destruction. Further, in the liquid crystal display device of the vertical alignment type, an MVA (Multi Vertical Alignment) method in which a projection for controlling the falling direction of the liquid crystal is formed on a TFT substrate or a color filter substrate is known, and a slit is formed in the slit. On the ITO (Indium Tin Oxide) electrode of the substrate, a PVA (Patterned Vertical Alignment) method for controlling the liquid crystal falling direction by an electric field, a substrate having a slit formed on the ITO electrode, and a light added thereto A PSA (Polymer Sustained A1 ignment) method in which a liquid crystal panel is formed by a liquid crystal of a polymerizable compound, an electric field is applied thereto, and ultraviolet rays (UV) or the like is applied to the liquid crystal in a state where the liquid crystal is dropped. The problem of the conventional vertical alignment method is that the cost of the panel using a complicated substrate is high, and the transmittance of a panel such as a protrusion or a slit is lowered. On the other hand, the liquid crystal alignment in the liquid crystal cell is imparted. Other means for the liquid crystal alignment energy of the film, it is known that a photosensitive film such as polyvinyl cinnamate or polyimine which has been formed on the surface of the substrate is irradiated with polarized or non-polarized radiation to impart alignment to the liquid crystal. The optical alignment method (refer to Patent Documents 1 to 8).

-6- S 201219450 This photo-alignment method is known to be useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal display device of a vertical alignment type, that is, it is known to be imparted by a photo-alignment method. The vertical alignment film of the alignment control force can uniformly control the tilt direction of the liquid crystal molecules at the time of applying a voltage (refer to Patent Documents 9 to 1 1). By using the vertical alignment film imparted with the alignment control force by the photoalignment method as described above, it is possible to tilt the liquid crystal molecules from the substrate normal direction toward one of the substrate faces with only the tilt. In this manner, the liquid crystal alignment film produced by the photo-alignment method is suitably used as a liquid crystal display element. However, when a liquid crystal alignment agent containing a cinnamic acid ester or a polyimine is known to be used in a photo-alignment method, there is a problem that a required amount of radiation irradiation is required with respect to the obtained liquid crystal alignment energy. The problem caused by the large amount of irradiation increases the increase in the tact time of the liquid crystal display element production, and causes defects in the liquid crystal alignment film due to the long-time exposure, which in turn leads to the reliability of the liquid crystal panel. reduce. Further, in the liquid crystal display device of the vertical alignment type, when the unreacted photoreactive group is present in the liquid crystal alignment film, the liquid crystal panel is exposed to the backlight (BL) light source for a long time, and the unreacted photoreactive group is exposed. There will be a reaction, and there is a problem such as a change in the pretilt angle of the liquid crystal. [PATENT DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 6-287453 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei No. Hei. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The object of the present invention is to provide a pretilt angle which can exhibit a polarized or non-polarized radiation by a small amount of irradiation. Further, even in the case of exposure to a backlight source for a long period of time, the liquid crystal alignment agent and the liquid to be used for maintaining the liquid crystal alignment film for the vertical alignment of the pretilt angle can be maintained. A crystal alignment film and a liquid crystal display element including the liquid crystal alignment film. [Means for Solving the Problem] As a result of intensive research to achieve the above object, the present inventors have found that a diamine compound having a specific novel structure is found to have reached a liquid crystal alignment treatment agent containing a polymer obtained by using the diamine compound. The above purpose. The present invention is based on this insight and has the following gist. (1) a liquid crystal alignment treatment agent containing polyamic acid,

-8-S 201219450 and a polymer of at least one of the group of polyamidiamine obtained by imidating the polyphosphonium amide; wherein the polyglycolic acid comprises the following formula The reaction of the diamine component of the diamine compound of [1] with the di-hepatic component of tetradecanoic acid; [Chemical 1] 〇

(wherein X1 is shown as a single bond, -ch2〇-, -〇-, _CC)C)_,_0CC)_, -NHCO-, or -CONH-, and X2 is shown as a carbon number of 1 to 3 , χ3 is shown as -0-, -ΝΗ-, or -NCR1) -, X4 is shown as a single bond, -〇-, -S-, or _ NH-. X5 is shown as a single bond or a carbocyclic ring selected from the group of the following formulas [X5-1] to [X5-5], and X6 is shown as a linear or branched alkyl group having a carbon number of 1 to 18'. A hydrogen atom, -R2, -OR3, -NHR4, -N(R5)2, or -SR6. Here, R1 to R6 are each independently shown as an alkyl group having 1 to 5 carbon atoms. η is shown as an integer of 1 or 2), [Chemical 2] [X5-2]

[X5-3]

[XS-5] (However, in the above carbocyclic structure, any hydrogen atom may be replaced by ch3). (2) The liquid crystal alignment treatment agent according to the above (1), wherein the content of the diamine compound of the formula [i] in the above-mentioned two-9-201219450 amine component is 30 to 100 mol% 〇(3) as described above (1) Or a liquid crystal alignment treatment agent of (2), wherein X3 of the above formula [1] is -〇·'χ7 is a hydrogen atom. (4) The liquid crystal alignment treatment agent according to any one of the above (1), wherein X5 of the above formula [1] is a single bond. (5) The liquid crystal alignment treatment agent according to any one of the above (1), wherein X1 of the above formula [1] is a single bond, and X4 is -0-. (6) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the η of the above formula [1] is 1. (7) The liquid crystal alignment treatment agent according to any one of the above (1), wherein X2 of the above formula [1] is -CH2-, and X6 is an alkyl group having 8 to 12 carbon atoms. (8) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above (1) to (7). (9) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above (1) to (7), which is provided with a liquid crystal alignment energy by irradiation of polarized light or non-polarized radiation. (10) A liquid crystal display device comprising the liquid crystal alignment film of (8) or (9) above. (11) a diamine compound represented by the following formula [1],

-10- S 201219450 【化3】 Η2Νγ^-Χ1-Χ2-Χ3 Η2Ν^

Χ4.χ5.χβ [1] (wherein χΐ is shown as a single bond '-CH20-, _0., -COO-, -OCO-, -NHCO-, or -CONH-, X2 is shown as carbon number 1~3 The alkyl group 'X3 is shown as .0·, -NH-, or _N(R丨)_, and X4 is shown as a single bond, -〇_, -S-, or _NH-. X5 is shown as a single bond or A carbocyclic ring selected from the group of the following formulas [X5-1] to [X5-5], and X6 is a linear or branched alkyl group having a carbon number of 1 to 18, which is represented by a hydrogen atom, -R2. -OR3, -NHR4, -N(R5)2, or -SR6. Here, R1 to R6 are each independently shown as an alkyl group having 1 to 5 carbon atoms. η is an integer of 1 or 2), [Chemical 4] [X5-!] [Χ5-2]

~CKD~ [X5-S] (However, in the above carbon ring structure, any hydrogen atom can be replaced by ch3). (12) A diamine compound according to the above (11), wherein X3 of the above formula [1] is -0-, and X7 is a hydrogen atom. (1 3 ) The diamine compound of the above (1 1 ) or (丨2), wherein X5 of the above formula [1] is a single bond. (1 4) The diamine compound of any one of the above (1 1 ) to (i 3 ) wherein X1 of the above formula [1] is a single bond, and X4 is -0-. The diamine compound according to any one of the above (11) to (14), wherein η of the above formula [1] is 1» (16) as in the above (11) to (15) Any one of the diamine compounds, wherein X2 of the above formula [1] is -CH2-, and X6 is an alkyl group having 8 to 12 carbon atoms. (17) A polyimine which is obtained by reacting a diamine component of the diamine compound according to any one of the above (1) to (16) with a tetracarboxylic dianhydride component. Or imidizing the polyphosphonium hydrazide to obtain the effect of the invention

In the liquid crystal alignment agent of the present invention, a liquid crystal alignment film for exhibiting a pretilt angle can be obtained by using a small amount of radiation irradiation compared to the conventional photoalignment method. Further, the liquid crystal display element ’ having the liquid crystal alignment film of the present invention can stably exhibit a pretilt angle even when exposed to a backlight source for a long period of time, and is useful as a liquid crystal display element having high reliability. [Best Mode of Carrying Out the Invention] <Diamine Compound of the Formula [1]> The diamine compound of the present invention (hereinafter also referred to as a specific diamine compound) is represented by the following formula [1].

S

[1] 201219450 【化5】

In the formula, X1 is represented by a single bond, _CH2o-, -ο-, -coo-, -oco-, -NHCO·, or -CONH-. X2 is shown as an alkylene group having a carbon number of 1 to 3. X3 is shown as _〇_, -NH·, or -NCR1)-. X4 is shown as a single bond, -0-, -S-, or -NH-. X5 is shown as a single bond or a carbocyclic ring selected from the group of the following formulas [X5-1] to [X5-5]. X6 is shown as a linear or branched alkyl group having 1 to 18 carbon atoms. X7 is shown as a hydrogen atom, -R2, -〇R3, -NHR4, -N(R5) 2, or _SR6. Here, R1 to R6 are each independently shown as an alkyl group having 1 to 5 carbon atoms. η is shown as an integer of 1 or 2. 【化6】

Pts-2]

[Χ5-5] In the carbocyclic structure of the above formula [X5-1] to [Χ5-5], any nitrogen atom may be substituted by ch3. The bonding position of the two amine groups (-NH2) in the formula [1] is not limited. Specifically, for example, the bonding group (X1) with respect to the side chain is the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, and the position of 3, 4 - 13- 201219450 Set, or 3, 5 position. Among these, the bonding position of the two amine groups is 2, 4, 2, from the viewpoint of the reactivity at the time of synthesizing polyamic acid and the easiness of synthesizing the diamine compound. The position of 5, or the position of 3, 5 is particularly good. When the diamine compound of the present invention is used as a liquid crystal alignment film for vertical alignment, the pretilt angle is imparted by irradiation of ultraviolet rays, and the portion represented by the following formula [2] contained in the formula [1] is Determine the part of the pretilt. By optimizing this configuration, a better pretilt angle can be obtained. 【化7】

In the formula [2], X1 is a single bond, a bond group of -CH20-, -0-, -COO., -OCO-, -NHCO-, or -CONH-, and X2 is a alkylene having a carbon number of 1 to 3. base. The length of the alkyl chain of X2 is important for exhibiting a pretilt angle with a small amount of irradiation, and if the alkyl chain is too long, the amount of irradiation until the pretilt angle is exhibited increases. This is because a photoreaction occurs at a portion of the base of the amine (from the portion of the above formula [2] bonded to the carbonyl group of X3) contained in the polymer forming the liquid crystal alignment film for vertical alignment. The anisotropy of the photoreaction affects the entire side chain, and thus the alignment control force imparted to the liquid crystal by the side chain becomes large. This result, even for a small amount of exposure, -14-

S 201219450 also makes it possible to exhibit the pretilt angle of the liquid crystal. In the formula [2], X3 is represented by -〇-, -NH-, or -NCR1)-, and X4 is represented by a single bond, -0-, -S-, or -NH-. R1 is shown as an alkyl group having 1 to 5 carbon atoms. X3 and X4 are the bonding groups of the photoreactive portion, and in terms of the wavelength of the light absorption wavelength of the photoreactive group or the ease of synthesis, X3 and X4 are particularly preferably -〇-〇[2], X5 It is a single bond or a carbocyclic ring selected from the group of the following formulas [xM] to [X5-5], and X6 is a linear or branched alkyl group having 1 to 18 carbon atoms. X5 and X6 are important for aligning liquid crystals vertically, and when X5 is a single bond, X6 is preferably a long-chain alkyl group in terms of vertical alignment energy. The carbon number of X6 in this case is preferably 6 to 18, more preferably 8 to 12. Further, when X5 is a carbon ring selected from the group of the following formulas [X5-1] to [X5-5], X4 is preferably a slightly shorter alkyl group in order to enhance the vertical alignment energy. In this case, the carbon number of X4 is preferably from 1 to 1, more preferably from 3 to 8.

-〇〇- [XS-5] In the formula [2], X7 is represented by a hydrogen atom, -R2, -OR3, -NHR4, -N(R5)2, or -SR6. Here, R2 to R6 are each independently shown as an alkyl group having 1 to 5 carbon atoms. η is shown as an integer of 1 or 2. X7 and η are important for determining the photoreactive wavelength of the photoreactive group -15-201219450 v • ..., if the electron-donating substituent is used in χ7, the absorption of photoreactive groups The wavelength will be longer wavelength. Also, if η is 2, the same effect will be obtained. X7 and η can make the photosensitive wavelength of the non-reactive group a preferred wavelength. From the viewpoint of the sensitivity of the vertical alignment 'photosensitive wavelength and photoreactivity when used in the liquid crystal alignment film', the preferred specific combinations of X1 to X7 of the formula [1] are as follows. 【化9】

[化10.]

-16- S 201219450

【化12】

-17- 201219450 【化13】

【化14】

【化15】

-18-

S 201219450 【化'16】

【化17】

【化18】

-19- 201219450 【化19】

-20- s 201219450 【化21】

201219450 【化23】

【化24】

S 201219450 【化25】

【化26】

In the CnH2n + 1 moiety described in the above-exemplified diamine compound, η is represented by an integer of from 1 to 18. <Synthesis method of specific diamine compound> Process 1 is produced by reacting acrylate body 2 obtained from dinitrogen 1 with benzene derivative 3 having a cleavable functional group in the side chain桂-23- 201219450 Dinitrogen 4 of the citric acid site. The obtained dinitrogen 4 can be carried out by selecting a reduction method which does not affect the double bond portion of the side chain, and it is possible to convert it to the intended diamine 5.

Method for Producing Compound 1 <X1 is a single bond (m is an integer of 1 to 3, and X3 is represented by -〇·, -NH-, or -NR1-) &gt; Several raw materials are commercially available. When it is difficult to obtain a commercially available product, when a borane reducing agent is used as a carboxylic acid as shown in the compound 6, a reduction reaction is carried out, and X3 is synthesized as a raw material corresponding to -〇. Further, when a boron-reducing agent is allowed to act on the compound of the compound 6 in which the carboxylic acid moiety is a cyano group, that is, the compound 7, the raw material of the diamine compound in which X3 is _NH_ can be synthesized. 【化28】

-twenty four-

S 201219450 After converting the hydroxyl group of the compound la' wherein X3 is -〇- into a leaving group such as a halogen or a sulfonate, even if the azide derivative obtained by reacting with the azide is reduced, X3 is -NH-compound la". Further, after conversion to a leaving group, after reacting with succinimide or phthalimide, the resulting N-alkyl sulfimine is treated with hydrazine. Decomposition, that is, a compound 1 a" in which X3 is -NH- can also be obtained by synthesis of an amine synthesized by Gabriel. For the compound la" wherein X3 is -NH-, an alkyl halide or an alkyl sulfonate is reacted in the presence of a base to obtain a compound wherein X3 is -NR1 (R1 is represented by an alkyl group having 1 to 5 carbon atoms). La". Further, the aldehyde compound acts to form a corresponding imine compound, and the imine moiety is reduced with a borane-based reducing agent or the like, that is, by using a reductive amination reaction, X3 is obtained as -NR1 (R1) The compound la"' is shown as an alkyl group having a carbon number of 1 to 5). In the case of alkylation of the former, although a by-product in which a plurality of alkyl groups are introduced can be obtained, the latter method has no by-products. The introduction of an alkyl group is effective. <X1 is ·〇- (m is an integer of 1 to 3 'X3 is shown as -0-, -NH-, or -NR1-) &gt; Available as a commercial product Dinitrophenol 8 is alkylated by a compound 9 having a protecting group P to obtain a dinitro group having a side chain 1 〇° The deprotecting group P contained in the dinitro group is deprotected' It can produce dinitro intermediate 1 b. -25- 201219450 【化29】

8 9 1〇 In the compound 9, Y is a halogen atom such as F, Cl, Br, I or the like, or a methanesulfonyloxy group, a benzenesulfonyloxy group, a toluenesulfonyloxy group, a trifluoromethanesulfonyl group, or the like. Sulfonates. The protective group P includes an ester-based protecting group such as a mercapto group, an ethyl fluorenyl group, a propyl fluorenyl group or a benzamidine group, a methoxymethyl group, an ethoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group. Acetal-based protecting group, trimethylsulfonyl, triethylsulfonyl, tris(isopropyl)decyl, triphenylsulfonyl, tert-butyldimethylhydrazino, tert-butyl A protecting group for an indenyl group such as a diphenylfluorenyl group or an isophenylpropyldiphenylfluorenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group, or a tert-butoxy group. A carbonate-based protecting group such as a carbonyl group. From the viewpoint of controlling side reactions, an acetal or sulfhydryl protecting group is preferred. In the reaction between the compound 8 and the compound 9 to obtain the dinitro group 10, in order to coexist with a base, an inorganic base such as potassium carbonate, sodium hydrogencarbonate, sodium hydride or potassium hydride or a triethyl group can be used as the base to be used. An amine, an amine such as di(isopropyl)ethylamine or the like. In the case of carrying out the reaction, in order to carry out the reaction smoothly, it is preferred to add sodium iodide, potassium iodide or tetra-n-butylammonium iodide. In the case of the deprotection reaction of the compound 10, it is carried out by selecting a deprotection condition suitable for the protective group to be used.

-26- S 201219450 When the base is protected, the liquid hydrolysis reaction of either acidic or alkaline is effective. Further, deprotection can also be carried out by a transesterification reaction with a lower alcohol. When an acetal protecting group is used, it is preferred to use a mineral acid or an organic acid such as formic acid, acetic acid or toluenesulfonic acid to remove the protective reaction using a catalytic amount. When a protecting group based on a fluorenyl group is used, it is preferably a deprotection of a fluoride using a tetra-n-butylammonium fluoride or the like under the same conditions as the deprotection of the acetal protecting group. The obtained X3 is a compound of -ΝΗ-, and by performing a reductive amination reaction, X3 can be synthesized into a compound lb corresponding to -NR1 (the alkyl group represented by R1 as a carbon number of 1 to 5). Further, a compound in which the above-mentioned compound 8 and the OH group of the compound 9 are replaced with a Y group, that is, a compound in which the hydroxyl group of the compound 8 is fluorine or chlorine, and the compound 9 is an OH group, the reaction is carried out in the presence of a base. It is also possible to obtain compound 1 〇. <X1 is -COO-, or -CONH- (m is an integer of 1-3, X3 is shown as -〇-, -NH-, or -NR1-) &gt;

By reacting a carboxylic acid or the derivative 11 with a compound 12 having a protecting group P, a dinitro-ester having a side chain 1 3 (Q = 0) or a dinitro-lutamine 13 is obtained. (Q is -NH-) » by protecting the dinitro-ester 13 (Q is -〇-), or dinitro-valeramine 13 (Q is -NH-) Deprotection, a dinitro intermediate having an ester bond group can be produced -27- 201219450

In the compound 11, Hal is an OH group or a halogen atom, and when stability is considered, a compound 11 having a hydrazine H group or a chloro group is preferably used. The protecting group P in the compound 12, preferably a protecting group, is also synonymous with the foregoing. Z in compound 12 is represented by a hydroxy 'amine group, a halogen, or a sulfonyl group. Q in the compound 13 is shown as -0-, or -NH-. The functional group represented by Z in the compound 12 is selected in consideration of the configuration of the Hal moiety of the compound 11 used. For example, Hal is an OH group, and if Z is an OH group or an NH 2 group, dicyclohexylcarbodiimide or 1-ethyl-3-(3-dimethylaminopropyl)carbon dioxime is used. When a condensing agent such as an imine or a carbonyldiimidazole is reacted, a compound 13 having an ester (Q is -〇-) or a guanamine combination (Q is -NH-) can be obtained. Hal is an OH group, and when a halogen or a sulfonyl group is selected as Z, an inorganic base such as potassium carbonate, sodium hydrogencarbonate, sodium hydride or potassium hydride, triethylamine or di(isopropyl)ethylamine is used. When the amine is reacted, the ester compound 13 (Q is -0-) can be obtained. In order to carry out the reaction smoothly, it is also effective to add sodium iodide, potassium iodide or tetra-n-butylammonium iodide.

When Hal is a halogen atom represented by a chloro group, and hydrazine in the compound 12 is a hydroxyl group or an amine group, an ester compound 13 (Q is -0-) or a guanamine compound 13 (Q is -NH-) can be obtained. ). This reaction is carried out by adding an amine such as triethylamine or pyridine as a base.

-28-S 201219450 By subjecting the obtained protecting group P of the compound 13 to deprotection, the compound 1 c can be obtained, and the conditions for deprotection are the same as those for the above compound 1 oxime. For the compound la" wherein X3 is -NH-, an alkyl halide or a sulfonate is reacted in the presence of a base to obtain a compound wherein X3 is NR1 (R1 is represented by an alkyl group having 1 to 5 carbon atoms). Further, the aldehyde compound acts to form a corresponding imine compound, and the imine moiety is reduced with a borane-based reducing agent or the like, that is, by using a reductive amination reaction, X3 is obtained as NR1. In the case of alkylation of the former compound lc» (wherein R1 is represented by an alkyl group having 1 to 5 carbon atoms), although a by-product of introducing a plurality of alkyl groups can be obtained, the latter method has no by-products. The introduction of an alkyl group is effective. <X1 is -OCO-, or -NHCO- (m is an integer of 1-3, X3 is shown as -0-, -NH-, or -NR-) &gt; The reaction of nitrophenol (Q is -〇-) or dinitroaniline (Q is -NH-) 14 with the carboxylic acid derivative 15 having a protecting group P to carry out esterification or oximation to become an ester Alternatively, a dinitro intermediate 1 d having an ester bond or a guanamine bond can be produced by deprotecting the dinitro group of the guanamine side chain by a 'protection group contained in the dinitro group 16'.

-29- 201219450 Q in compound 14, dinitroso 16, and dinitro intermediate Id is shown as -0 or -NH-. In the carboxylic acid derivative 15, Hal is shown as an OH group or a halogen atom, but in consideration of stability, a compound having an OH group or a chlorine group is preferably used. 15 A preferred protecting group of the protecting group P is also synonymous with the foregoing. .

Hal is an OH group, i.e., when carboxylic acid 15 is reacted with dinitrophenol 14 (Q is -0-) or dinitroaniline 14 (Q is -NH-), generally using dicyclohexyl carbon dioxime A condensing agent such as an imine or 1-ethyl-3-(3.dimethylaminopropyl)carbodiimide or carbonyldiimidazole. Further, it is preferred to add a catalytic amount of acid or N,N-dimethylaminopyridine for the reaction. It is also preferred to carry out the reaction by using an acid halide derivative represented by a chlorine group or the like, and a reaction such as an amine such as triethylamine or pyridine is added thereto. By deprotecting the protecting group P of the obtained compound 16, a dinitro intermediate 1 d can be obtained, and the conditions for deprotection are the same as those of the above compound 10. The compound 2 of the compound 2 It can be produced by esterification between the corresponding raw material 1 such as dinitrobenzyl alcohol and an acrylic acid derivative. As the acrylic acid derivative, an acid halide such as an acryl chloride or an acrylate bromide or an acrylic anhydride is preferably used. In the esterification reaction, as the base, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, NaH, KaH, or the like can be used. Inorganic base, trimethyl-30-z 201219450 amine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, Colin An organic base such as an amine such as a base, tert-sodium butoxide or tert-potassium butoxide. The solvent can be appropriately selected as long as it is inert under the reaction conditions, stable, and does not interfere with the reaction. For example, an amine, an aprotic polar organic solvent (dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), an ether (diethyl) can be used. Ether, diisopropyl ether, tert butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic Hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane) Alkane, etc., lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be selected in consideration of the reaction conditions, the ease of production, and the like, and can be used alone or in combination of two or more. Further, as the case may be, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is preferably in the range of from -100 °C to the boiling point of the solvent used, more preferably in the range of -50 to 150 °C. The reaction time is preferably from 0.1 to 1,000 hours. The compound 2 obtained as described above can be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. Further, 'Compound 2 can also be transesterified with an acrylate such as methyl acrylate or ethyl acrylate and dinitrobenzyl alcohol, or acrylic acid with bis-31 - 201219450 benzyl chloride, dinitro The reaction of dinitrobenzyl halide such as benzyl bromide is carried out to synthesize the compound 3 method [Chem. 32]

L-Xs-X6 γ·\|/·υ • X? Jn 17 3 In the above compounds 17 and 18, 'halogen atoms, such as F, Cl, Br, I, etc., -〇Η, -SH, or -NH2' X5 is shown as a single bond or a carbocyclic ring selected from the group of [X5-1] to [X5-5], and X6 is shown as a linear or branched alkyl group having a carbon number of 1 to 18. X7 is shown as a hydrogen atom, -R2, -OR3, -NHR4, ·(R5)2, or -SR6. Here, R2 to R6 are exclusive to each other and are not a hospital base having a carbon number of 1 to 5. η is shown as an integer of 1 or 2. Υ and L are each independently a halogen or a pseudohalogen. For example, it is represented by F, C1, Br, I, methanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy, trifluoromethanesulfonyl, and the like. Alkylsulfonyloxy, or aromatic sulfonyloxy. The method for producing the compound 3 can be produced by, for example, a reaction of a compound represented by 17 with a compound represented by oxime 8. Further, a few of the compounds 17 and the compound 18 are easily obtained as a commercial product. When X4 is -0-, -S-, or -NH->

-32- S 201219450 The substituent U of compound 1 7 is -OH, -SH, or -NH2, and X5 of compound 18 is a single bond or is selected from the group of [X5-l]~[X5-5] In the case of a carbocyclic ring, the compound 2 is obtained by reacting the two compounds in the presence of a base. As the base to be used, for example, a hydroxide or carbonate of an alkali metal such as lithium, sodium, potassium or the like, triethylamine, dicyclobicyclooctane, dinonicycloundecene, pyridine, 4-dimethyl An organic aliphatic, aromatic, or heterocyclic organic base such as a guanylpyridine. Mixtures of such bases can also be used. Particularly preferred is potassium carbonate. The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, a ketone solvent (acetone, 2-butanone, methyl isobutyl ketone, etc.), an aprotic polar organic solvent (dimethylformamide, dimethyl hydrazine, dimethyl acetamide) can be used. , N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, ter t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons Classes (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), teeth Prime hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles ( Acetonitrile, propionitrile, butyronitrile, etc.). The solvent can be appropriately selected in consideration of the ease of production of the reaction, etc., and can be used alone or in combination of two or more. Further, a dehydrating agent or a desiccant may be used as a non-aqueous solvent, as the case may be. The reaction temperature is preferably -100 ° c to the boiling point of the solvent used, more preferably in the range of -5 0 to 150 ° C. -33- 201219450 The reaction time is preferably from 0.1 to 1,000 hours. The compound 3 obtained as described above can be purified by recrystallization, distillation, hydrazine gel column chromatography or the like. The substituent U of the compound 17 is -OH, -SH, or -ΝΗ2, and when the X5 of the compound 18 is a single bond or [Χ5-5], the metal complex and the coordination can be carried out in the presence of a suitable base. The base is used as a catalyst to synthesize the compound 3 by a coupling reaction. As the metal complex, a copper complex, a palladium complex, or a nickel complex is preferably used. In particular, it is preferred to use a zero-valent complex which uses a tertiary phosphine or a tertiary phosphite as a ligand. Further, in the reaction system, an appropriate precursor which can be easily converted into a zero-valent complex can also be used. Further, in the reaction system, a complex which does not contain a tertiary phosphine or a tertiary phosphite as a ligand may be mixed with a tertiary phosphine or a tertiary phosphite, and a tertiary phosphine or a trisole may be produced. The grade of phosphorous acid acts as a low valence complex of the ligand.

As the tertiary phosphine or tertiary phosphite of the ligand, for example, triphenylphosphine, tris-fluorenyltolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2·double (diphenylphosphino)ethane, iota, bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphine) As the ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphoric acid or the like, two or more kinds of complexes containing such a ligand may be suitably used. As the catalyst, a copper complex or a palladium complex which does not contain a tertiary phosphine or a tertiary phosphite can be used. Further, it is also preferred to use a complex containing a tertiary phosphine or a tertiary phosphite in combination with the above-mentioned ligand. As a complex which does not contain a tertiary phosphine or a tertiary phosphite used in combination with the above ligand, the copper catalyst is CuCl, CuBr, Cul, Cu20, CuCN, CuO-34-s 201219450, etc. Palladium catalysts are bis(benzylideneacetone)palladium, bis(benzylideneacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium, palladium acetate, palladium chloride, chlorine Palladium-acetonitrile complex, palladium-activated carbon, and the like. Further, as a complex containing a tertiary phosphine or a tertiary phosphite as a ligand, for example, dimethylbis(triphenylphosphine)palladium or dimethylbis(diphenylmethylphosphine)palladium, (ethylene) bis(triphenylphosphine)palladium, ruthenium (triphenylphosphine)palladium, bis(triphenylphosphine)dichloropalladium or the like is not limited thereto. The amount of the copper complex, the palladium complex, the nickel complex or the like used as the catalyst may be a so-called amount of the catalyst, and it is usually sufficient to make the reaction compound 20 mol% or less, usually 10 Mole% or less. As the base, in addition to sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid, etc., inorganic base, methylamine, dimethyl Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropyl An amine, a butylamine, a dibutylamine, a tributylamine, a diisopropylethylamine, a pyridine, an imidazole, a quinoline, a colin base, etc., may also be used, such as sodium acetate or potassium acetate. The hydrazine such as lithium acetate may be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane-35-201219450, heptane , petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen hydrocarbons (chloroform, dichloromethane, Carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be selected in consideration of the reaction conditions, the ease of production, and the like, and can be used alone or in combination of two or more. Further, as the case may be, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is -100 ° C to the boiling point of the solvent to be used, preferably in the range of -50 to 150 ° C. The reaction time is preferably 〇. 1 to 1,000 hours. The compound 3 obtained as described above can be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. &lt; When X4 is a single bond> The substituent U of the compound 17 is F, Cl, Br, or I, and when X4 of the compound 3 is a single bond, the metal complex and the coordination can be utilized in the presence of a suitable base. Compound 3 is synthesized as a coupling reaction of a catalyst. As the metal complex, an iron complex, a palladium complex, or a nickel complex is preferred. It is particularly preferred to use a tertiary phosphine or a tertiary phosphite as a zero-valent complex of a ligand. Further, in the reaction system, an appropriate precursor which can be easily converted into a zero-valent complex can also be used. Further, in the reaction system, a complex which does not contain a tertiary phosphine or a tertiary phosphite as a ligand may be mixed with a tertiary phosphine or a tertiary phosphite, and a tertiary phosphine or a trisole may be produced. Grade of phosphorous acid as a low base of ligand

-36- S 201219450 Subvalent complex. A tertiary phosphine or a tertiary phosphite as a ligand, for example, triphenylphosphine, trioxo-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2·double (diphenylphosphino)ethane ' ι,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, ι,ι'_bis(diphenylphosphine) As the ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphoric acid or the like, two or more kinds of complexes containing such a ligand may be suitably used. As the catalyst, an iron complex or a palladium complex which does not contain a tertiary phosphine or a tertiary phosphite can be used. Further, it is also preferred to use a complex compound containing a tertiary phosphine or a tertiary phosphite, in combination with the above-mentioned ligand. As a complex which does not contain a tertiary phosphine or a tertiary phosphite used in combination with the above ligand, the iron catalyst is FeBr3, FeBr2, FeCl3, FeCl2, FeF3, FeF2.

Fe (acetylacetonato) 3, Fe (acetylacetonato) 2, etc., in terms of catalysts are bis(benzylideneacetone)palladium, ginseng (benzylideneacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile) ) palladium dichloride, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, etc. Further, as a complex containing a tertiary phosphine or a tertiary phosphite as a ligand, for example Such as dimethyl bis(triphenylphosphine)palladium, dimethylbis(diphenylmethylphosphine)palladium, (ethylene)bis(triphenylphosphine)palladium, ruthenium (triphenylphosphine)palladium, bis ( Triphenylphosphine, dichloropalladium or the like is not limited thereto. The amount of the iron complex, the palladium complex, the nickel complex or the like used as the catalyst may be a so-called amount of the catalyst, and it is usually sufficient to make the reaction compound 20 mol% or less, usually 10 Mole% or less. As the base, in addition to sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate -37-201219450, sodium hydrogencarbonate, potassium hydrogen phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid, etc. - dimethylethylene diamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, Isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colin base, etc. In addition to the amines, sodium acetate, potassium acetate, lithium acetate or the like can also be used. The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (dimethylformamide, dimethyl hydrazine, dimethylacetamide, hydrazine-methylpyrrolidone, etc.), ethers can be used. Classes (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether) Etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, tetrachlorinated) Carbon, dichloroethane, etc., lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be selected in consideration of the ease of production and the like, and can be used alone or in combination of two or more. Further, depending on the case, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is -100 ° C to the boiling point of the solvent to be used, preferably in the range of -50 to 150 ° C. The reaction time is preferably from 0.1 to 1, hrs. -38-

S 201219450 The compound 3 obtained as described above can also be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. Process for Producing Compound 4 Compound 4' can be synthesized by a coupling reaction of a Heck reaction or the like in the presence of a compound of a metal complex, a ligand, and a base. As Y in the compound 3, a substituent having a dissociable ability can be used, for example, a halogen atom such as F, Cl or Br' I, a methanesulfonyloxy group, a benzenesulfonyloxy group or a toluenesulfonyloxy group can be used. The alkylsulfonyloxy group, the aromatic sulfonyloxy group or the like of a group such as a trifluoromethanesulfonyl group or the like is preferably Br, I or a trifluoromethanesulfonyl group when the reactivity is considered. The coupling reaction is preferably carried out by using a metal complex and a ligand as a catalyst. Usually, as the metal complex, a palladium complex, a nickel complex or the like is used. As the catalyst, although various builders can be used, it is preferred to use a so-called low valence palladium complex or a nickel complex, in particular, a zero valence using a tertiary phosphine or a tertiary phosphite as a ligand. The complex is better. Further, an appropriate precursor which can be easily converted into a zero-valent complex can be used in the reaction system. More 'in the reaction system' can also be mixed as a ligand which does not contain a tertiary phosphine or tertiary phosphorous acid' with a tertiary phosphine or tertiary phosphite, and will produce a tertiary phosphine or three a phosphinic acid as a ligand of a lower valence complex 〇 as a ligand for a tertiary phosphine or a tertiary phosphite, for example, for example, tri-39-201219450 phenylphosphine, tolylphosphonium phosphine, diphenyl Methyl phosphine, phenyl dimethyl phosphine, I, 2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenyl) Styrene), butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphoric acid, etc., can also be suitably used to contain such a mixture Two or more complexes of a ligand. As a catalyst, it is preferable to combine a palladium complex which does not contain a tertiary phosphine or a tertiary phosphite and/or a complex containing a tertiary phosphine or a tertiary phosphite with the above ligand. To use. As a complex which does not contain a tertiary phosphine or a tertiary phosphite used in combination with the above ligand, for example, bis(benzylideneacetone)palladium, ginseng (benzylideneacetone)dipalladium, bis(acetonitrile) Dichloropalladium, bis(benzonitrile)dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, and the like. Further, as a complex containing a tertiary phosphine or a tertiary phosphite as a ligand, for example, dimethylbis(triphenylphosphine)palladium or dimethylbis(diphenylmethylphosphine)palladium, (ethylene) bis(triphenylphosphine)palladium, iridium (triphenylphosphine)palladium, bis(triphenylphosphine)dichloropalladium or the like, but is not limited thereto. The amount of the palladium complex to be used may be a so-called amount of the catalyst, and is usually sufficient to make the reaction compound 20 mol% or less, usually 10 mol% or less. As a test 'except inorganic test or methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, different Propylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colin base, etc. Other than the amine, sodium acetate, potassium acetate, lithium acetate or the like can also be used. -40-

S 201219450 is a solvent, and may be appropriately selected as long as it does not interfere with the reaction under the reaction conditions. Water, alcohols, amines, aprotic polar organic solvents ( dimethyl azorun, dimethyl acetamide, N-methylpyrrol (diethyl ether, diisopropyl ether, tert-) Butylmethyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons, heptane, petroleum ether, etc., aromatic hydrocarbons (benzene, methylated xylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetra Hydronaphthalenes (chloroform, dichloromethane, carbon tetrachloride, dichloroethylene fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). The reaction conditions may be selected as the same, or may be used alone or in combination of two or more. The dehydrating agent or the desiccant may be used as the non-aqueous solvent. The reaction temperature is - l〇〇. °C~ the boiling point of the solvent used is 1 5 (the range of TC. The reaction time is preferably 0.1 to 1, 〇〇〇 hours. The compound 4 obtained as described above can also be re-ruthenium gel column chromatography. Purification of activated carbon, etc. The preparation method of the compound 5 is carried out by selecting the double bond as the dinitrogen 4 obtained above. The reaction conditions are reduced to carry out the reduction of the nitro group to the desired diamine compound 5. Stable, inert, for example, dimethylformamide or the like can be used, ether ether, cyclopentylmethyl (pentane, hexane) Benzene, xylene, etc., halogen system, etc., lower ester, methyl propionate solvent, can be selected, in this case, it can also be, preferably -5 0~ crystal, distillation, no damage And the side chain 'can be converted to -41 - 201219450 For the reduction of the double bond of the side chain as the original nitro group, it is preferred to use a metal such as Fe, Sn, Zn or the like, together with the proton source The metal and the metal salt can also be used as a monomer or a combination. As the proton source, an acid such as hydrochloric acid, an ammonium salt such as ammonium chloride, or a protic solvent such as methanol or ethanol can be used. It can be used in an environment under a reducing atmosphere, and an aprotic polar organic solvent (dimethylformamide, dimethyl amide, dimethylacetamide, N-methylpyrrolidone, etc.) can be used. Ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, Amyl hydrocarbons (tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorine) Benzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile) The solvent may be selected in consideration of the reaction conditions, the ease of production, and the like, and may be used alone or in combination of two or more. Further, an appropriate dehydrating agent or desiccant may be used as the case may be. The reaction temperature is -100 ° C to the boiling point of the solvent to be used, preferably in the range of -50 to 150 ° C. The reaction time is preferably from 0.1 to 1,000 hours. The compound 5 obtained as described above can also be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. Method 2 - 42-

S 201219450 By reacting the dinitrogen 1, with the acrylic acid derivative 19 or the acid halide compound 20, a dinitrogen matrix 4 having a side chain having a cinnamic acid moiety can be produced. The dinitrogen compound 4' thus obtained can be converted into the target diamine compound 5 by selecting a reduction method which does not affect the double bond portion of the side chain and is carried out. 【化33】

Method for preparing compound 20

In the compound 19 and the compound 20, X is represented by halogen, F, Cl, Br, or I, and X4 is shown as a single bond, -0-, -S-, or -NH-. X5, X6, X7, and η are synonymous with the foregoing. The compound 20 is prepared by reacting the compound 19 with an acid halogenating agent - 43 - 201219450. χ ′ is preferably C1 or Β 观点 from the viewpoint of availability of the reagent and reactivity. As the acid halogenating agent to be used, for example, sulfoxide, chloroform, phosgene, chlorine, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, bismuth imidate , boron trichloride, sulfinium bromide, oxalic acid bromine, bromine, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide, bismuth imidate and N-bromosuccinate. Preferably, sulfinium chloride or sulfoxide is used. The acid halogenating agent is usually used in an amount of 2 to 1,000 moles, preferably 2 to 30 moles, more preferably 2 to 3 moles per mole of the compound 19. The above reaction can be carried out in an acid dentate agent such as sulfinium chloride, and a solvent can be used as needed. The solvent is not particularly limited as long as it is inert to the reaction, and for example, an aprotic polar organic solvent (dimethylformamide, dimethylammonium, dimethylacetamide, N-methyl) can be used. Alkyl pyrrolidone, etc., ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane Alkane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene 'dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, Dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile) Wait). These solvents can be selected in consideration of the ease of production of the reaction, etc., and can be used alone or in combination of two or more. Further, an appropriate dehydrating agent or desiccant may be used as the non-aqueous solvent, as the case may be. Moreover, the above reaction can be carried out without a catalyst, but by adding a touch-44-

S 201219450 The medium can reduce the amount of chlorinating agent used and accelerate the reaction. The catalyst is not particularly limited. For example, an organic base such as triethylamine, pyridine, porphyrin, N, N-dimethylaniline or dimethylformamide, sodium methoxide or the like is used. a metal alkoxide such as potassium oxy or potassium t-butoxide. Preferred examples are triethylamine pyridine and dimethylformamide. Further, more preferably, for example, pyridine. These catalysts are usually used in an amount of from 0 to 100 moles, preferably from 1 to 10 moles, per mole of the acid halide. The reaction temperature is -100 ° C to the boiling point of the solvent to be used, preferably in the range of -5 0 to 150 ° C. The reaction time is usually 〇. 1~1,0 0 0 hours. Further, the compound 20 obtained as described above can also be purified by an operation such as recrystallization, distillation, hydrazine gel column chromatography or the like. Method 1 of Compound 1 9 [Chem. 35]

3 21

In compound 21 'A is shown as alkyl, mercapto or hydrogen, such as methyl, ethyl, propyl, η-butyl, isopropyl, Urt-butyl, sec-butyl, phenyl, benzyl , mercapto, tetrahydropyranyl, tetrahydrofuranyl, methoxymethyl, methoxyethoxy, vinyl, and the like. The above reaction ' is a compound 19 obtained by coupling a compound 3 and 21 in the presence of a metal complex catalyst, a -45-201219450 group and a base, by a Heck reaction or the like. The reaction conditions are the same as those shown in the synthesis method of the compound 4 of Process 1. When A is an alkyl group or a mercapto group, after the reaction, the ester group -COOA can be derivatized into the corresponding compound 19 by hydrolysis of water in the presence of an acid or a base. The acid to be used may, for example, be a mineral acid such as dilute sulfuric acid or an organic acid such as p-toluenesulfonic acid, formic acid or acetic acid. Further, examples of the base include carbonates such as potassium hydrogencarbonate, sodium hydrogencarbonate, potassium carbonate, and sodium carbonate; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; calcium hydroxide and magnesium hydroxide; a hydroxide of an alkaline earth metal, a phosphate such as sodium dihydrogen phosphate or potassium dihydrogen phosphate, a carboxylate such as sodium acetate or potassium acetate, an organic base such as triethylamine or pyridine, or a methoxy group. Metal alkoxides such as sodium hydride and sodium ethoxide, metal hydrides such as sodium hydride, and the like. The hydrolysis may be carried out in a solvent mixed with water in order to smoothly carry out the reaction, and as the solvent to be used, for example, dimethylformamide, dimethylhydrazine or dimethylacetamide may be used. A protic polar organic solvent, a nitrile such as acetonitrile, propionitrile or butyl nitrile, an organic weakly alkaline solvent such as pyridine, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butyl An alcohol such as an alcohol or tert-butanol. Further, by heating, the reaction can be carried out more rapidly. The reaction temperature is -1 ° ° C to the boiling point of the solvent used, preferably in the range of -50 to 150 ° C. The reaction time is usually from 0.1 to 1,000 hours. Further, the compound 1.9 obtained as described above can also be purified by an operation such as recrystallization, distillation, hydrazine gel column chromatography or the like.

S 201219450 Formulation of Compound 19-2

【化36】 OHC

X4-Xs-X6 22 +

In the compound 22 and the compound 23, X4, X5, X6, Χ7, η, and Α are synonymous with the above. Moreover, the basis of the example shown in Α is also the same as described above. The method for producing the compound 19, for example, when A is an alkyl group or a fluorenyl group, a method in which the compound 22 and the compound 23 are dehydrated and condensed in the presence of a base, and the diester portion is hydrolyzed to decarbonate. Further, when A is hydrogen, there is a method in which the compound 22 and the compound 23 are dehydrated and condensed in the presence of a base to decarbonate. When A is hydrogen, it is not particularly limited. For example, in the presence of piperidine in a pyridinated solvent, the reaction is carried out at 60 to 100 ° C to dehydrate and condense the aldehyde group and malonic acid, and then, by using The reaction is carried out by heating to 100 to 150 ° C to carry out the decarbonation reaction to obtain a compound 19. The base to be used in the dehydration condensation reaction is not particularly limited as long as it is a base having a strength (basicity) of a base which allows the reaction to proceed smoothly. For example, lithium, sodium, potassium base metal hydroxide or carbonate, lithium decylamine, sodium amination, potassium alkoxide alkali metal amide, lithium hydride, sodium hydride, potassium hydride alkali metal hydrogenation , alkaline earth metal, sodium or potassium methanolate, ethanolate, η-propanolate, isopropanolate, η-butanolate, sec- -47- 201219450 butanolate, tert-butanolate, 2 -methyl-2-butanolate, 2-methyl-2-pentanolate, 3-methyl-3-pentanolate, 3-ethyl-3-pentanolate, by-grade, secondary or Organics of alkali metal alkoxides derived from aliphatic alcohols having a carbon number of 1 to 10, dicyclobicyclooctane, dioxodicycloundecene, 4-dimethylaminopyridine, pyrrolidine, piperidine, etc. Aliphatic, aromatic, heterocyclic nitrogen base. These bases can also be used as a mixture. As the base, sodium ethoxide or sodium hydride is preferred. The amount of the base to be used is usually 0.1 to 10 moles, preferably 1 to 5 moles per mole of the compound 22. The solvent can be used as long as it does not react with the compound 22 and the compound 23. For example, an aprotic polar organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide or N-methylpyrrolidone, diethyl ether or diisopropyl ether can be used. , ethers such as tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc., aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, benzene, toluene, and An aromatic hydrocarbon such as toluene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene or tetrahydronaphthalene; a nitrile such as acetonitrile, propionitrile or butyronitrile; or an organic weakly alkaline solvent such as pyridine or quinoline. Wait. Further, an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol or tert-butanol can also be used. These solvents can be selected in consideration of the ease of production of the reaction, etc., and can be used alone or in combination of two or more. Further, as the case may be, a suitable dehydrating agent or drying agent may be used as the nonaqueous solvent. The hydrolysis conditions of water are the same as those shown in Process 1 of Compound 19. The reaction temperature is -100 ° C ~ the boiling point of the solvent used, preferably -50 to -48-

S 201219450 1 5 0 °C range. The reaction time is usually 0.1 to 1, 〇〇〇 hours. Further, the compound 丨9 obtained as described above can also be purified by an operation such as recrystallization, distillation, hydrazine gel column chromatography or the like. Method for preparing compound 22 [Chem. 37] L-Xs-X6

In the compound 24, U and η are synonymous with the above. The method of producing the compound 22 is, for example, a method of reacting the compound 24 with the compound 18. Further, several of the compound 24 and the compound 18 can be easily obtained as a commercial product. The substituent U of the compound 24 is -OH, -SH, or -ΝΗ2, and the X5 of the compound 18 is a single bond or a carbocyclic ring selected from the group of the above [Χ5-1] to [X5-4], in the base In the presence of 'reaction of compound 24 with compound 18', compound 22 can be obtained. The reaction conditions can be applied to the method of the synthesis of the compound 3 of Process 1, wherein X5 is a structure selected from the group of the above [X5-1] to [Χ5-4]. The substituent ϋ of the compound 24 is -OH, -SH, or -ΝΗ2, and the X5 of the compound 18 is a single bond, or the carbon ring of the above [χ5_5] 'in the presence of a base' can be obtained by The ligand is combined as a coupling reaction of the catalyst -49-201219450. The reaction conditions can be applied to the method in the synthesis of the compound 3 of the process 1 in which the 'X5 is the above-mentioned [Χ5-5]. The substituent U of the compound 24 is halogen F, Cl, Br, or I. When X4 of the compound 22 is a single bond, in the presence of a base, a coupling reaction of the metal complex with a ligand as a catalyst can be carried out. And to synthesize. The reaction condition ' can be applied to the method for synthesizing the compound 3 of the method 1, and the method for the case where X4 is a single bond.

In the compound 25, A is synonymous with the above, and the examples are also the same as described above. The method for producing the compound 19 is, for example, a method in which the ester group -COO A is hydrolyzed with water after the dehydration condensation reaction of the compound 22 and the compound 25 in the presence of a base. The base to be used in the above reaction is not particularly limited as long as it is a base having a strength (basicity) of a base which makes the reaction smooth. For example, lithium, sodium, potassium alkali metal hydroxide, lithium decylamine, sodium amination, potassium alkoxide alkali metal amide, lithium hydride, sodium hydride, potassium hydride alkali metal hydride, alkaline earth a metalloid, sodium or potassium methoxide, ethanolate, n-

-50- S 201219450 propanolate, isopropoxide, n-butanolate, sec-butanolate, tert-butanolate, 2-methyl-2-butanolate, 2-methyl-2- Alkali metal derived from a primary alcohol of a primary, secondary or tertiary carbon number of 1 to 10, such as a pentoxide, a 3-methyl-3-pentanolate or a 3-ethyl-3-pentanolate Alcohol compounds and the like. These bases may also be used as a mixture as a base, preferably sodium ethoxide or sodium hydride. These bases are usually used in an amount of 0.1 to 10 moles, preferably 0.1 to 5 moles, per mole of the compound 22. The solvent can be used as long as it does not react with the compound 22 and the compound 25. For example, an aprotic polar organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide or N-methylpyrrolidone, diethyl ether 'diisopropyl ether can be used. An ether such as tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran or dioxane, an aliphatic hydrocarbon such as pentane, hexane, heptane or petroleum ether, benzene, toluene, xylene, and the like. An aromatic hydrocarbon such as toluene, chlorobenzene, dichlorobenzene, nitrobenzene or tetrahydronaphthalene; a nitrile such as acetonitrile, propionitrile or butyronitrile; or an organic weakly alkaline solvent such as pyridine or quinoline. Further, an alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol or tert-butanol can also be used. These solvents can be selected in consideration of the ease of production and the like, and can be used alone or in combination of two or more. Further, depending on the case, an appropriate dehydrating agent or desiccant may be used as the non-aqueous solvent. The hydrolysis conditions of water are the same as those shown in Process 1 of the compound 19. The reaction temperature is -l〇〇. The boiling point of the solvent to be used is preferably in the range of -50 to 150 °C. -51 - 201219450 The reaction time is usually 0.1 to 1,000 hours. Further, the compound 169 obtained as described above can also be purified by recrystallization, distillation, hydrazine gel column chromatography or the like. Process for the preparation of compound 19 - [Chem. 39]

X7 η In the compound 26, A is synonymous with the foregoing, and the examples are also the same as described above. W is triphenylphosphine or a phosphonate. The method of producing the compound 19, for example, a method of hydrolyzing hydroxy-C 0 0 A after reacting the compound 22 with the compound 26 in a Wittig reaction or a Horner-Wadsworth-Emmons reaction. The reaction is preferably carried out using a base in a solvent. For the test of the reaction, it is preferred to use a base which gives the phosphonium ylide a smooth strength. As the base, for example, a hydroxide or carbonate of a lithium, sodium or potassium base metal, a butyllithium, a sec-butyllithium, a tert-butyllithium-like alkyllithium, a lithium decylamine or an amine can be used. Sodium, potassium alkoxide, metal amide, lithium hydride, sodium hydride, potassium hydride, alkali metal hydride, lithium hexamethyldiazepine, sodium hexamethyldisodium azide, hexamethyl Alkaloids such as disilazide, alkaline earth metals, sodium or potassium methanolates, ethanolates, η-propanolates, isopropoxides, η-butanolates, sec- Butanolate, tert-butanolate, 2-methyl-2-butanolate, 2-methyl-2-pentanolate, 3-methyl-3-pentanolate, 3-B-52-

S 201219450 Alkyl-3-pentoxide, an alkali metal alkoxide derived from a primary, secondary or tertiary aliphatic alcohol having 1 to 10 carbon atoms, dinonicyclooctane, dinonicycloundecene, An organic aliphatic, aromatic or heterocyclic nitrogen base such as 4-dimethylaminopyridine, pyrrolidine or piperidine. In particular, butyl lithium or tert-butyl lithium is preferred. The solvent ' can be used as long as it does not react with the compound 22 and the compound 26. For example, 'ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar organic solvents (dimethylformamide) can be used. Amines 'dimethyl hydrazine, dimethyl acetamide, N-methyl pyrrolidone, etc.), aliphatic hydrocarbons (pentane, hexane 'heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene , toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be selected in consideration of the ease of production and the like, and can be used alone or in combination of two or more. Further, a dehydrating agent or a desiccant may be used as a nonaqueous solvent, as the case may be. The hydrolysis conditions of water are the same as those shown in Process 1 of Compound 19. The reaction temperature is -10 ° C to the boiling point of the solvent used, preferably in the range of _50 to 150 ° C. The reaction time is 0.1 to 1, 〇〇〇 hr. Further, the compound 1 9 ' obtained as described above can also be purified by an operation such as recrystallization, distillation, hydrazine gel column chromatography or the like. -53- 201219450 Formulation of Compound 19-5 [Chemical 40]

X4-x5-x6 &quot;χ5&quot;χ6+

Χ4-χ5-χ6 In the compound 27 and the compound 28, X4, X5, X6, X7, and η are synonymous with the above. Antimony is an organometallic reactant of Li, MgCl, MgBr' or Mgl. A is synonymous with the foregoing, and the base of the example is also the same as described above. The method for producing the compound 19, for example, by mixing the compound 27 with a copper salt, a zinc salt or a dialkyl zinc in a solvent to prepare a cuprate or a diaryl zinc compound, and then performing a compound represented by the compound 28, 4-After adding the reaction, the ester group-C 00 A is hydrolyzed by water. The copper salt, zinc salt or dialkylzinc used in the reaction may be used singly or in combination with such a copper salt, a zinc salt or a dialkyl zinc. Examples of the copper salt used in the reaction include a mixed salt of CuCl, CuBr, Cul, CuCN, or CuCl^LiCl, and particularly preferably Cul. Further, as an example of the zinc salt used for the reaction, there are ZnCl2, ZnBr2, or Znl2, and particularly ZnCl2. As an example of the dialkylzinc used in the reaction, there may be dibutylzinc, diethylzinc or dibutenylzinc, and particularly preferably diethylzinc. The solvent can be used as long as it does not react with the organometallic reactant. For example, ethers (diethyl ether, diisopropyl ether, tetrabutyl) can be used.

S-54- 201219450 methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar organic solvent (dimethylformamide, dimethyl sulfoxide, dimethyl acetamide) , N-methylpyrrolidone, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, two Chlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.). These solvents can be selected in consideration of the ease of production of the reaction, and the like, and can be used alone or in combination of two or more. Further, as the case may be, a suitable dehydrating agent or desiccant may be used as the nonaqueous solvent. The hydrolysis conditions of water are the same as those shown in Process 19 of Compound 19. The reaction temperature is -100 ° C to the boiling point of the solvent to be used, preferably in the range of -50 to 150 ° C. The reaction time is 0 · 1 to 1, 0 0 0 hours. Further, the compound 10 obtained as described above can also be purified by an operation such as recrystallization, distillation, hydrazine gel column chromatography or the like. Method for preparing compound 27

In the compound 29 and the compound 30, U, X, X4, X5, X6, X7, and η are synonymous with the above. -55-201219450 A method of producing Compound 27, for example, a method of synthesizing Compound 30 by the reaction of Compound 29 with Compound 18, followed by reacting Compound 30 with metallic magnesium or a lithiating agent. Several of the compound 29 and the compound 18 can be easily obtained as a commercial product. The substituent U of the compound 29 is -OH, -SH, or ΝΗ2, and the X5 of the compound 18 is a single bond, or the above [X5-l When the carbocyclic ring selected by the group [~5-4] is reacted with the compound 18 in the presence of a base to obtain the compound 3 0 reaction condition, the compound 3 in the process 1 can be obtained. In the synthesis method, X5 is a method in which the carbon ring selected from the group of the above [X5-l] to [Χ5-4] is applied. The substituent U of the compound 29 is ·OH, -SH, or -ΝΗ2, and when X5 of the compound 18 is a single bond or the above-mentioned carbocyclic ring of [Χ5-5], in the presence of a base, the metal may be misaligned The compound and the ligand are synthesized as a coupling reaction of a catalyst. The reaction conditions can be applied to the method in the synthesis method of the compound 3 of Process 1 wherein X 5 is the above [Χ 5-5]. When the substituent U of the compound 29 is halogen F, Cl, Br, or I', when X4 of the compound 27 is a single bond, in the presence of a base, a coupling reaction of the metal complex with a ligand as a catalyst can be carried out. And to synthesize. The reaction conditions' can be applied in the method of synthesizing the compound 3 of Process 1, and X4 is a single bond. With respect to the obtained compound 30, a metal Mg was added to an ether solvent to carry out a reaction, and a compound 27 (M = MgF, MgCl, MgBr, Mgl) which can be used for the Grenj reaction was obtained. Further, in the solvent, lithium metal is reacted to obtain a compound 27 in which ruthenium is Li. -56-

S 201219450 Preparation of Compound 19-6 [Chem. 42]

L-x5-x6 18 -X4~XS-X6 1 X7 Jn In the compound 31, U and n are synonymous with the above. The method for producing the compound 19 is, for example, a method in which the compound 3丨 is reacted with the compound 18, and after the reaction, the ester group-COOΑ is hydrolyzed by water. Further, several of the compound 31 and the compound 18 can be easily obtained as a commercial product. The substituent U of the compound 31 is -OH, -SH, or -NH2, and the X5 of the compound 18 is a single bond or a carbocyclic ring selected from the group of the above [X5-1] to [X5-4], in the case of a base In the presence of the compound 31, the compound 31 is reacted with the compound 18, and after the reaction, hydrolysis with water as shown in Process-1 of the compound 19 is carried out to obtain the compound 19. The reaction conditions can be applied to the method of synthesizing the compound 3 of Process 1, wherein X5 is a carbocyclic ring selected from the group of the above [X5-1] to [X5-4]. The substituent U of the compound 31 is -OH, -SH, or ΝΗ2, and when X5 of the compound 18 is a single bond or the above [Χ5-5], the metal complex and the ligand are used as a ligand in the presence of a base. The catalyst is subjected to a coupling reaction 'after the reaction' to obtain a compound 19 by performing hydrolysis in water as shown in Process 1 of Compound 19. The reaction conditions can be applied to the method in the synthesis method of the compound 3 of Process 1 wherein χ5 is the above [Χ, 5]. -57- 201219450 The substituent U of compound 31 is halogen F, Cl, Br, or I. When X4 of compound 19 is a single bond, the metal complex and the ligand are coupled as a catalyst in the presence of a base. After the reaction, the reaction is carried out by hydrolysis of water as shown in Process-1 of Compound 19 to give Compound 19. The reaction condition ' can be applied to the method in which the compound X of the method 1 is a single bond. Process for Producing Compound 4 Compound 4 can be produced by esterification reaction of Compound 1 with Compound 19 of the acrylic acid derivative or Compound 20 in a solvent. Particularly in the reaction of the acid halide such as the compound 20 with the compound 1, the acid halide is preferably an acid halide such as an acid chloride or an acid bromide, and more, in the alkali The reaction is carried out in the presence of a smooth reaction. As the base, for example, inorganic substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid planer, sodium hydride, potassium hydride or the like can be used. Alkali, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, colin base, etc., tert - an organic base such as sodium butoxide-tert-potassium butoxide. The solvent "is stable as long as it is stable under the reaction conditions, and does not interfere with the reaction, and can be suitably selected. For example, an amine, an aprotic polar organic solvent (dimethylformamide, dimethylhydrazine, dimethylacetamide, N-methylpyrrolidone, etc.), an ether (diethyl) can be used. -58-

S 201219450 ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum acid, etc.), Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, two Ethyl chloride (etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be selected in consideration of the reaction conditions, the ease of reaction, and the like, and can be used alone or in combination of two or more. Further, depending on the case, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is -100 ° C to the boiling point of the solvent used, preferably in the range of -50 to 15 ot. The reaction time is preferably from 0.1 to 1,000 hours. The compound 4 obtained as described above can also be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. Further, in the reaction of the compound 19 with the compound 1, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, carbonyldiimidazole or the like is used. The condensing agent is general. In this case, it is preferred that the amount of the catalyst or the addition of N,N-dimethylaminopyridine is effective for the progress of the reaction. Process for Producing Compound 5 The production of Compound 5 using Compound 4 can be carried out by the method described in Process 1. 201219450 &lt;polyglycine, polyphthalate, polyimine&gt; The diamine compound of the present invention is obtained by using tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic dianhydride or the like. The carboxylic acid or the derivative is reacted to obtain a polylysine having a specific structure in a side chain. Further, in addition to the tetracarboxylic acid or the derivative, the reaction of the tetracarboxylic acid diester dichloride with the diamine compound or the presence of the tetracarboxylic acid diester and the diamine compound in the presence of a condensing agent, a base or the like is used. The reaction provides a polyamidomate of the polyimide precursor. Further, by dehydrating the polyglycolic acid, or by heating the polyglycolate at a high temperature and promoting the dealcoholization to form a ring closure, a polyimine having a specific structure in the side chain can be obtained. &lt;Polyuric acid&gt; The polylysine of the present invention is a polyamic acid obtained by a reaction of a diamine component containing a diamine compound represented by the formula [1] with a tetracarboxylic dianhydride. The polyglycolate of the present invention is obtained by reacting a diamine component containing a diamine compound represented by the formula [1] with a tetracarboxylic acid diester dichloride in the presence of a base, or a tetracarboxylic acid. The diester and the diamine compound are reacted in the presence of a condensing agent, a base or the like to obtain a polyglycolate. The polyimine of the present invention is a polyimine obtained by dehydration of the polyamine or by heating the ring closure of the polyphthalate. Polyglycine, polyphthalate and polyimine are useful as polymers for obtaining liquid crystal alignment films. For obtaining a polyamine of polylysine by reaction with tetracarboxylic dianhydride

-60- S 201219450 The content of the component (hereinafter, also referred to as diamine component) of the diamined compound represented by the formula [1] is not limited. formula〔;! The ratio is, for example, more than or equal to 2% by mole of the diamine component, more preferably 2% by mole or more, and still more preferably 30% by mole or more. The 1% molar % of the diamine component may be a diamine compound represented by the formula [1]. When the proportion of the diamine compound represented by the formula [i] is larger, the ability to stand the liquid crystal vertically becomes higher when the liquid crystal alignment film is formed, and the efficiency of the optical alignment treatment becomes higher. According to the structure of the side bond of the formula [1], or the vertical alignment energy of the liquid crystal, since the pretilt angle during the photoalignment treatment changes, in order to obtain the desired pretilt angle, the formula [1] does not The content ratio of the diamine compound can be selected within a preferred range. In the diamine component, the diamine compound represented by the formula [1] is used in the case of less than 100% by mole, although a diamine compound other than the diamine compound represented by the formula [1] (also referred to as other diamine) The compound) is not particularly limited, and when the specific example is exemplified, it is as follows. Examples of the alicyclic diamines include, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4 '_Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like. Examples of the aromatic diamines include 0-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, and 3,5. -diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-P-xylene, 1,3-diamino-4-chlorobenzene, 3,5 -diaminobenzoic acid, 1,4-diamino 2,5-dichlorobenzene, 4,4,-diamino-1,2-diphenylethane, 4,4'-diamino -2,2,-dimethylbibenzyl, 4,4,-diaminodiphenylmethane, 3,3'-diamino-61 - 201219450 diphenylmethane, 3,4'-diamino Diphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminopurine, 4,4'-diaminopurine, 4,4 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenyl maple, 4,4'-diaminodiphenyl ketone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic 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)phenyl]anthracene, bis[4-(4-aminophenoxy) Phenyl] maple, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, 9,9-double (4-Aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiyl Phenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino onion peptide, 1,3-diamine Base, 1,6-diaminoguanidine, 1,8-diaminoguanidine, 2,7-diaminoguanidine, 1,3-bis(4-aminophenyl)tetramethyldioxane, Benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-double (4 -amine phenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminephenyl) Heptane, 1,8-bis (4-aminophenyl) Octane, 1,9-bis(4-aminophenyl)decane, 1,1 fluorene-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane

-62- S 201219450 , 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenyloctane, 1,9·bis(4-aminophenoxy) ) decane, 1,10-bis(4-oxy)decane, dimethyl bis(4-aminophenyl)propane-1,3-dicarboxylate 4-aminephenyl)butane-1,4- Dimethyl dicarboxylate, di(4-aminophenyl: dimethyl 1,5-dicarboxylate, bis(4-aminophenyl)hexane-1,6-diacid di-di(4-aminophenyl) Dimethyl heptane-1,7-dicarboxylate, dimethyl 2-(4-aminophenyl benzene-1,8-dicarboxylate, bis(4-aminophenyl)decane-1,9-diacid, two (4-Aminophenyl)nonane-1,10-dicarboxylic acid dimethyl ester, 1,3-bis[aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-amine) Phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)benzenepentane, 1,6-bis[4-(4-aminophenoxy)phenoxy Hexane, [4-(4-aminophenoxy)phenoxy]heptane, 1,8-bis[4-(phenoxy)phenoxy]octane, 1,9-bis[4] -(4-Aminophenoxyoxy) decane, 1,1 fluorene-bis[4-(4-aminophenoxy)phenoxy, etc. As an example of the aromatic-aliphatic diamine, for example, 3-aminobenzyl 4-amine Amine, 3-amino-N-methylbenzylamine, 4-amino-N-ylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-benzene Ethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropylamine, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl) 4-(3-Methylaminopropyl)aniline, 3-(4-aminobutyl) 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)benzene (4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline 5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, oxy)amine Benzobenzene, bis(pentane-methyl ester, yl)octyl dimethyl ester 4-(4-phenoxyoxy) 1,7-bis 4-amino)phenyl]nonanylamine, methylbenzyl N -methyl)phenyl)aniline aniline, amine, 4-, 4-(4-(5--63-201219450 methylaminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, etc. as a heterocyclic diamine For example, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-three Bismuth, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2 , 5·bis(4-aminophenyl)-1,3,4-oxadiazole, etc. As an example of the aliphatic diamine, for example, 1,2-diaminoethane, 1,3-diamine Propane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Octane, 1,9-diaminodecane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2, 5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamine 3-methyl heptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2- Bis(3-aminopropoxy)ethane' and the like. A diamine compound having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a large cyclic substituent formed therefrom may also be used. Specifically, a diamine represented by the following formula [DA-1] to formula [DA-26] can be exemplified. 【化43】

-64 -

S 201219450 (r6 is the base of the carbon number 1~22 or the fluorine-containing yard base)°

(s 5 is shown as -(:00-,-0(:0-, -〇0-----;^(:0-, -〇112-,-0-, -CO-, or -NH-) R6 is shown as an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(s6 is represented by -0-, _OCH2-, -CH20-, -COOCH2-, or -CH2OCO-, and R7 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group) . 【化46】

OCO (S7 is not -COO-, CONH-, -NHCO--65- 201219450 COOCH2-, -CH2OCO-, -CH20-, -OCH2-, or -CH2-, R8 is an alkyl group having 1 to 22 carbon atoms, Alkoxy, fluoroalkyl or fluoroalkoxy). 【化47】

Η2Ν· NH, 'SeO~0~R9 [DA-16] (s8 is shown as - COO-, -OCO-, -CONH-, -NHCO-, -cooch2-, -CH2OCO-, -CH20-, -OCH2- , -CH2-, -O-^ or -NH-, R9 is fluoro, cyano, trifluoromethyl, nitro, azo, methyl, ethyl, ethoxy, or hydroxy) . 【化48】

NH2

η力Λ

[DA-19]

Rio

R10 (Rio is an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene, respectively, is a trans-body).

-66- S 201219450 【化49】 Ο

tX〇 h2n

[DA-17]

【化50】

【化51】

Simultaneously with the diamine compound of the general formula, the diamine compound of the above [DA-1] to [DA-26] may be used for the purpose of compensating for the vertical alignment of -67 to 201219450. As a more preferable diamine, in terms of voltage holding ratio or residual storage voltage, it is preferred that the formula [DA-10] to [DA-26] is more preferably [DA-10]~[ DA-16] diamine compound. The content of the diamine compound is preferably 5 to 50 mol%, more preferably 5 to 30 mol%, based on the diamine component, although it is not particularly limited. Further, the following diamine compound can also be used. 【化52】

[DA· 28]

[DA-29] ,nh2 € [DA-30]

NH2

uaCH.XNXr '(CH2)n [DA-34] can increase the voltage holding ratio (VHR) by including [DA-27] or [DA-28], because [DA-29]~[DA-34] It is suitable for the reduction of stored charge. Further, a diamine-based oxazide or the like represented by the following formula [DA-27] can also be exemplified as another diamine compound.

-68- S 201219450 【化53】

(m is an integer from 1 to 10). The other diamine compound may be used in combination of one or two or more kinds depending on the properties of the liquid crystal alignment, the voltage-holding property, and the storage charge in the case of forming a liquid crystal alignment film. The tetracarboxylic dianhydride which reacts with the diamine component in order to obtain the polyglycolic acid (polyglycolic acid) of the present invention is not particularly limited. The following is an example of this specific example. As a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4·tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic 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- Naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ',4,4'-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene- 1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.02'5]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, six Ring [6.6.0.12'7.03'6.19'14.01()'13]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 4-(2,5- Dihydrotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like. -69- 201219450 In addition to the tetracarboxylic dianhydride having the above alicyclic structure or aliphatic structure, when an aromatic tetracarboxylic dianhydride is used, the liquid crystal alignment property is improved and the storage charge of the liquid crystal cell can be obtained. Reduced, it is appropriate. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3,4,4,-biphenyltetracarboxylic dianhydride, and 2,2',3,3'·biphenyl. Tetracarboxylic dianhydride, 2,3,3,4-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3, , 4-diphenyl ketone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl) dianhydride, ι, 2, 5, 6 - naphthalenetetracarboxylic dianhydride, 2.3.6.7-naphthalenetetracarboxylic dianhydride, and the like. The dicarboxylic acid dialkyl ester which is reacted with the diamine component in order to obtain the polyphthalate of the present invention is not particularly limited. The following is an example of this specific example. As the aliphatic tetracarboxylic acid diester, for example, dialkyl 1,2,3,4-cyclobutanetetracarboxylate, 1,2-dimethyl-1,2,3,4-cyclobutane IV Dialkyl carboxylic acid '1,3-Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, iota, 2,3,4-tetramethyl-1,2, Dialkyl 3,4-cyclobutanetetracarboxylate, dialkyl 2,3,4-cyclopentanetetracarboxylate, dialkyl 2,3,4,5-tetrahydrofuran tetracarboxylate , i, 2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3 , 4-tetrahydro-1-naphthalene succinate dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3,3, fluorene] octane - 2.4.6.8- Dialkyl carboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentyl acetate, cis-3,7 -Dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.〇2,5]decane-3,4,7 , 8-tetracarboxylic acid-3,4: 7,8-dialkyl ester,hexacyclo[ 6.6.0.12,7.〇3, 6.19,14.〇丨〇'13]hexadecane-4,5, 11,12_tetracarboxylic acid-4,5-70-

S 201219450 : 11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran_3_yl 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, etc. As a dialkyl aromatic tetracarboxylate, for example, dimethoate diester, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2',3,3 ,-dialkyldicarboxylate, 2,3,3',4-biphenyltetracarboxylic acid dialkyl 3,3',4,4'-diphenyl ketone tetracarboxylic acid dialkyl ester , 2,3,3,4-diphenyldicarboxylate, bis(3,4-dicarboxyphenyl)ether dialkyl vinegar, 3.4-dicarboxyphenyl)decane dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, and the like. The dicarboxylic acid used to obtain the polyfluorene of the diamine compound of the present invention as a raw material to react with the diamine component is not particularly limited. Specific examples of the aliphatic dicarboxylic acid of the di or the derivative include, for example, malonic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, hexamethylene, bismuthic acid, and 2-methyl group. A dicarboxylic acid such as adipic acid, trimethyl adipic acid, pimelic acid, dimethyl glutaric acid, 3,3-diethyl succinic acid, sebacic acid or sebacic acid. Examples of the dicarboxylic acid having an alicyclic structure include 1,1·cyclopropene bis- 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, hydrazine, and 2 ring-rings. Acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dimethanol 2.4-diphenyl-l,3-cyclobutanedicarboxylic acid, 1-ring Butene diunsaturated cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, hydrazine, cyclopentaic acid, 1,3-cyclopentanedicarboxylic acid, 1, 1-cyclohexanedicarboxylic acid, L2-cyclohexanecarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, iota, 4-(decene) dicarboxylic acid, Decalene-2,3-dicarboxylic acid, bicyclo [2.2.2] xinyuan?) * alkyl phenyl ester, ketone tetra bis (ester amide, carboxylic acid, diacid 2,2-, octyl carboxylate Acid-carboxylic acid, '1-dicarboxyalkane-2-low-1,4-71-201219450 dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-di Oxy-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3.3] Heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphor acid, etc. As the aromatic dicarboxylic acid, for example, hydrazine -phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5 -hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6- Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 1,4- onion peptide dicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-linked Phenyl dicarboxylic acid, 1,5-extended biphenyl dicarboxylic acid, 4,4"-biphenyldicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Ethylene dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4, 4'-bibenzyldicarboxylic acid, 4,4'-indole dicarboxylic acid, 4,4'-diphenylethylenedicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl Dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetate, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene Acrylic acid, 3,3'-[ 4,4'-(methylenebis-P-phenylene)dipropionic acid, 4,4'-[ 4,4'-(oxydi-P-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-P-phenylene)]butyric acid, (isopropylene) a bis-P-phenylene dioxy)dibutyric acid, bis(P-carboxyphenyl)dimethyl decane, etc. As the dicarboxylic acid containing a heterocyclic ring, for example, 1,5-(9-oxonium) Dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4 -dicarboxylic acid, 1,2,5-oxadiazole-3,4-72-

S 201219450 dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid The various dicarboxylic acids described above, such as 3,5-pyridinedicarboxylic acid, may also be acidic dihalides or anhydrides. Among these dicarboxylic acids, in particular, a dicarboxylic acid capable of imparting a polyamine of a linear structure is preferable in terms of maintaining the alignment of the liquid crystal molecules. Among them, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4,2-biphenyldicarboxylic acid, 4,4'-diphenylmethane are preferably used. Carboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2,2-double (Phenyl) propane dicarboxylic acid, 4, 4 cast triphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridinedicarboxylic acid or the like. Also present in these compounds are heterologous or mixtures containing such. Further, two or more kinds of compounds may be used in combination. The dicarboxylic acid used in the present invention is not limited to the compounds exemplified above. The tetracarboxylic dianhydride may be one or more selected from the group consisting of liquid crystal alignment, voltage retention characteristics, and storage charge when the liquid crystal alignment film is formed. When the polyglycine of the present invention is obtained by the reaction of a tetracarboxylic dianhydride with a diamine component, a conventional synthesis means can be used. It is generally a method of reacting a tetracarboxylic dianhydride with a diamine component in an organic solvent. The reaction of the tetracarboxylic dianhydride with the diamine compound is relatively easy to carry out in an organic solvent, and is advantageous in that no by-products are produced. The organic solvent-73-201219450 which is used for the reaction of the tetracarboxylic dianhydride and the diamine compound is not particularly limited as long as the produced polylysine is dissolved. The following is an example of this specific example. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylene Indamine, dimethyl hydrazine, tetramethyl urea, samarium, dimethyl hydrazine, hexamethylarylene, r-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene , Ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cyproterone, ethyl cyanidin, methyl cyanisol Acetate, ethyl cyproterone acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl Ether, 3-methyl-3-methoxyethoxy Acid ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyl ester, butyl ether , diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, η-hexane, η-pentane, η-octane, diethyl ether, cyclohexanone, ethylene Carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propyl propionate, methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 methoxy propyl Acid propyl ester, -74-

S 201219450 3-methoxypropionic acid butyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-indole, hydrazine-dimethylpropane decylamine, 3 - Ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, and the like. These can be used alone or in combination. Further, even a solvent in which polylysine cannot be dissolved can be used in combination with the above solvent within a range in which the produced polyamine does not precipitate. Further, the water in the organic solvent hinders the polymerization reaction, and further, since it causes hydrolysis of the produced polylysine, it is preferred to use the organic solvent as far as possible. When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, for example, a solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is added as it is, or A method in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a method of adding a diamine component to an organic solvent as a solution in which a tetracarboxylic dianhydride component has been dispersed or dissolved is exemplified. As a method, a method of adding a tetracarboxylic dianhydride component and a diamine component alternately, etc., any of these methods can be used. Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of compounds, the reaction can be carried out in a state of being mixed beforehand, or the reaction can be carried out in an individual order, or the individual reaction can be carried out. The low molecular weight body is subjected to a mixing reaction to form a high molecular weight body. The polymerization temperature at this time may be any temperature of from -20 to 150 t, preferably from -5 to 100 °C. Further, although the reaction can be carried out at any concentration, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction liquid becomes too high, and the viscosity is excessively stirred. -75-201219450 The mixing becomes difficult, so the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter, an organic solvent can be added. In the above reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably from 0.8 to 1.2, more preferably from 0.9 to 1.1. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polylysine becomes. The polyimine of the present invention is useful as a polymer for obtaining a liquid crystal alignment film by dehydrating a ring closure of the above polyamic acid. In the polyimine of the present invention, the dehydration ring closure ratio of the proline group (the imidization ratio) is not necessarily 100%, and may be arbitrarily adjusted depending on the purpose or purpose. &lt;Polyimine&gt; As a method for imidating polyphosphonium amide, for example, a solution of polylysine is heated and heated by imidization, and a catalyst is added to polyamine. The catalyst solution of the acid solution is imidized. The temperature at which the polyaminic acid is thermally imidized in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, and the water formed by the imidization reaction is excluded to the outside of the system. The method to be carried out is suitable. The catalyst of the polyaminic acid is imidized, and the basic catalyst and the acid anhydride are added to the solution of the polyamic acid at a temperature of -20 to 250 ° C, preferably 〇 180. (: stirring is carried out. The amount of alkaline catalyst is 0. 5 of the proline group)

-76- S 201219450 〜30 moles, preferably 2 to 20 moles; the amount of the anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amidate group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., among which pyridine is preferred because it has a moderate alkalinity for the reaction. . The acid anhydride may, for example, be acetic anhydride, trimellitic anhydride or pyromellitic dianhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is easy, and therefore it is preferable. The imidization ratio of the imidization of the oxime by the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. &lt;Polyurethane&gt; As a method of synthesizing a polyphthalate, by reacting a tetracarboxylic acid diester dichloride with a diamine compound, or a tetracarboxylic acid diester with a diamine compound, The reaction is carried out in the presence of a solvent, a base or the like to obtain a polyglycolate which is one of the precursors of the polyimine. Alternatively, the polyglycolic acid ester can be obtained by polymerizing polylysine in advance and esterifying the carboxylic acid in the lysine by a polymer reaction. Specifically, the tetracarboxylic acid diester dichloride and the diamine compound are allowed to react in the presence of a base and an organic solvent at -20 to 150 ° C, preferably 0 to 50, for 30 minutes. It can be synthesized in 2 hours, preferably 1 to 4 hours. As the base, ruthenium pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used for the purpose of stable reaction, and pyridine is preferred. The amount of the base to be added is easily removed, and it is easy to obtain a high molecular weight body. From the viewpoint of -77 to 201219450 to tetracarboxylic acid diester dichloride, preferably 2 to 4 moles. When the polycondensation reaction is carried out in the presence of a condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-dimethylaminopropyl)carbodiimide salt can be used. Acid salt, N,N'-carbonyldioxazol, dimethoxy-1,3,5-trimethylmethylmorphine, 0-(benzotriazol-1-yl)-&gt; ^1,]^',:^'-Tetramethylurea tetrafluoroborate, 0-(benzoquinone-1-yl)-N,N,N',N,-tetramethylurea hexafluorophosphate , (2,3-dihydro-2-bromo-3-benzo D-azolyl) phosphonic acid diphenyl, 4-(4,6-dimethoxy-n% trianthylene-2-yl 4-methoxymorpholine chloride-n-hydrate and the like. Further, in the method of using a condensing agent, when a Lewis acid is added as an additive, the reaction proceeds efficiently. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of the Lewis acid added is preferably 0.1 to 1.0 moles per mole of the tetracarboxylic acid diester. The solvent used in the above-mentioned polymerization to obtain the poly-proline is used as the solvent. The solubility of the monomer and the polymer is preferably Ν-methyl-2-pyrrolidone or butyrolactone. Wait. These solvents can be used alone or in combination of two or more. Further, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyglycolate is preferably as far as possible. In the reaction solution, the total concentration of the tetracarboxylic acid diester dichloride and the diamine component is less likely to cause precipitation of the polymer, and it is preferably from 1 to 30% by mass, more preferably from the viewpoint of easily obtaining a high molecular weight body. It is 5 to 20% by mass. Furthermore, the reaction is carried out in a nitrogen atmosphere to prevent the incorporation of outside air.

S 201219450 &lt;Polyuramine&gt; Polyamide can also be synthesized in the same manner as polyglycolate. &lt;Recovery of Polymer&gt; The resulting polyglycine, polyglycolate, and poly are formed from a reaction solution of polyglycine (polyglycolic acid), polyphthalate, or polyamidiamine. When recovering ruthenium or the like, the reaction solution may be placed in a weak solvent to precipitate a polymer. Examples of the weak solvent used for the precipitation include methanol, acetone, hexane, butyl cyanidin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which has been precipitated in a weak solvent is filtered and recovered, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, when the polymer recovered by precipitation is repeated for 2 to 10 times to be redissolved in an organic solvent and subjected to reprecipitation recovery, impurities in the polymer can be reduced. As the weak solvent at this time, for example, an alcohol, a ketone, a hydrocarbon or the like is used. When three or more kinds of weak solvents selected from the above are used, the efficiency of purification is further improved. When the molecular weight of the polyamic acid and the polyimine contained in the liquid crystal alignment treatment agent of the present invention is considered to be the strength of the coating film obtained, the workability at the time of formation of the coating film, and the uniformity of the coating film, GPC is used. The weight average molecular weight measured by the (Gel Permeation Chromatography) method is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000 » &lt;Liquid crystal alignment treatment agent&gt; -79 - 201219450 The liquid crystal alignment treatment agent of the present invention is A coating liquid for forming a liquid crystal alignment film in which a solution of a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a polymer selected from at least one of the polymers of the present invention. In this case, the content of the resin component is preferably from 1 to 20% by mass, more preferably from 3 to 15% by mass, even more preferably from 3 to 10% by mass. In the present invention, the resin component may be all the polymer of the present invention, or may be a polymer other than the polymer of the present invention. In this case, the content of the polymer other than the polymer of the present invention in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass. The other polymer, for example, as a tetracarboxylic acid The diamine component to be reacted with the anhydride component is, for example, polyamine or polyimine obtained by using a diamine compound other than the specific diamine compound. The organic solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. The following is an example of this example. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl maple, hexamethylarylene, 7-butyrolactone, 3-methoxy —N,N-Dimethylpropane decylamine, 3-ethoxy-indole, hydrazine-dimethylpropane decylamine, 3-butoxy-hydrazine, hydrazine-dimethylpropane decylamine, 1,3- Dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate Ester, digan

-80- S 201219450 Methyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination. The liquid crystal alignment agent of the present invention may contain components other than the above. In this case, a solvent or a compound which improves film thickness uniformity or surface smoothness, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like are applied when the liquid crystal alignment agent is applied. Specific examples of the solvent (weak solvent) for improving the uniformity of the film thickness or the surface smoothness are as follows. For example, isopropyl alcohol, methoxymethylpentanol, methyl cyproterone, ethyl cyproterone, butyl cyproterone, methyl cyproterone acetate, ethyl cyproterone acetate, butyl Kikabi alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol single Acetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3- Methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3·methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, acetic acid pentane Ester, butyl butyl ester, butyl ether, diisobutyl ketone 'methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, η-hexane, n-pentane, η-octane Second Ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate 'ethyl pyruvate, 3-methoxypropionic acid Ester, 3-ethoxypropionic acid-81 - 201219450 methyl ethyl ester, ethyl 3-methoxypropionate 3- 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropene Acid propyl ester, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-benzene Oxyl 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2 - (2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate and other solvents with low surface tension Wait. These weak solvents can be used in one type or in a mixture of plural kinds. When the solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyoxyn-based surfactant, and a nonionic surfactant. More specifically, for example, F-Top EF301, EF3 03, EF3 5 2 (manufactured by Tokem Products Co., Ltd.), MEGAFACE F1 7 1 , F173, R-30 (manufactured by DIC Corporation), Fluorad FC43 0, FC43 1 (Sumitomo 3M company), AashiGuard AG710, Surflon S-3 82, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 1 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. As a specific example of the compound which improves the adhesion between the liquid crystal alignment film and the substrate, for example, a functional decane compound or a ring-containing compound is shown below.

-82- S 201219450 Oxygen compounds, etc. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymercaptopropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxyindolyl-1,4,7- Trioxane, 10-triethoxyindolyl-1,4,7-trioxane, 9-trimethoxyindolyl-3,6-dimercaptoacetate, 9-triethoxy Mercapto-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-benzene 3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N - bis(oxyethylene)-3-amine Propyl triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, Mu&gt;^,&gt;^',^^,-tetraglycidyl-111-xylenediamine, 1,3-bis(]^,;--diglycidyl Aminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. Further, in addition to the adhesion between the substrate and the film, the liquid crystal alignment treatment agent may contain a phenoplast-based additive as described below for the purpose of preventing deterioration of the electrical characteristics of the backlight - 83 - 201219450. The specific phenolic plastic additive is as follows, but is not limited to this configuration. 【化1】

In the case of using a compound which improves the adhesion to the substrate, the amount of use is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. When the amount of use is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected; if it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated. In the liquid crystal alignment treatment agent of the present invention, in addition to the above, the dielectric properties of the liquid crystal alignment film may be changed so as not to impair the effects of the present invention, and dielectric properties may be added. For the purpose of improving the hardness or density of the film formed into a liquid crystal alignment film, a crosslinkable compound may be added. &lt;Liquid crystal alignment film and liquid crystal display element&gt; Liquid crystal alignment of the present invention The treatment agent is applied to the substrate and calcined, and then subjected to alignment treatment by rubbing treatment or light irradiation, or in vertical alignment -84 -

S 201219450 It can be used as a liquid crystal alignment film without alignment treatment when it is used. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency. A glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed, from the viewpoint of simplification of the procedure. Further, in the case of the reflective liquid crystal display device, if it is only a single-sided substrate, an opaque material such as a germanium wafer or the like may be used. In this case, a material such as aluminum or the like may be used. Although the coating method of the liquid crystal alignment treatment agent is not particularly limited, industrially, there are generally screen printing, lithography, quick-drying printing, injection, and the like. As another coating method, there are also a dipping, a roll coater, a slit coater, a spin coater, etc., and these may be used depending on the purpose. The liquid crystal alignment treatment agent is applied to the substrate and calcined, and is heated at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate to evaporate the solvent to form a coating film. When the thickness of the coating film formed after calcination is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, since the reliability of the liquid crystal display element is lowered, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the film after calcination is treated by rubbing or polarized ultraviolet rays. In the liquid crystal display device of the present invention, a liquid crystal display cell is produced by a known method using a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention. For example, when one example of liquid crystal cell fabrication is made, it is exemplified that a pair of substrates having a liquid crystal alignment film formed by -85-201219450 is prepared, and a spacer is spread on a liquid crystal alignment film of a single substrate, and a liquid crystal alignment film is formed. The surface is bonded to the other substrate, the liquid crystal is injected under reduced pressure, and the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer has been dispersed, and then the substrate is bonded and attached. The method of sealing, etc. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμηη. As described above, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention can be suitably used for a large-screen, high-definition liquid crystal television or the like in order to be excellent in reliability. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. 【化55】 ΟΗ

2 &lt;Example 1 &gt; 4-Iodophenol 1 (22.0 g, 〇.l〇〇mol), potassium carbonate (20.7 g, 0.150 mol), and dimethylformamide! 30 ml (ml) was placed in a four-necked flask, stirred under a nitrogen atmosphere, and then warmed to 80 °C. After reaching 80 ° C, 1 bromo broth (17.9 g, 〇. 〇 8 〇 9 mol) was dripped for 30 minutes, and after the completion of the dropping, the mixture was further stirred for 1 hour. After the disappearance of 1-bromodecane was confirmed by GC (gas chromatography) -86 - 201219450, the solvent was distilled off, and 120 ml of toluene and 150 g of pure water were added for extraction, and the aqueous layer was removed. Thereafter, 100 ml of 1N NaOH was placed in the organic layer for extraction, and the aqueous layer was removed. The obtained organic layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was obtained by filtration, and the obtained organic layer was distilled off under reduced pressure to give Compound 2 (26.9 g, 0.0747 mol, yield). 92.3%). The structure of Compound 2 was confirmed by 1H-NMR (nuclear magnetic resonance) analysis. ^-NMR (CDC13): δ 7.5 5 -7.52 (m, 2H, Ar-H), 6.69-6.65 (m, 2H, Ar-H), 3.90 ( t, 2H, J = 6.8 Hz, Ar-O- CH2), 1.79-1.72 (m, 2H, Ar-0-CH2-CH2-), 1.47- 1.27 (m, 14H, Ar-0-CH2-CH2-C7H14-), 0.87 (t,3H,J= 6.8 Hz, -CH2-CH3). 【化56】

3 4 &lt;Example 2 &gt; A solution of 3,5·dinitrobenzyl alcohol 3 (39.6 g, 0.200 mol), triethylamine (26.3 g, 0.260 mol), and tetrahydrofuran in 200 ml was mixed in nitrogen. Under an atmosphere, the mixture was stirred at 〇 ° C. A solution of acryl chloride (21.7 g, 0.240 mol) and 40 ml of tetrahydrofuran was added dropwise for 30 minutes. Further, after the dropwise addition, the mixture was stirred for 4 hours. After the completion of the reaction, the solvent was distilled off, and 300 g of water was placed in the obtained crude product -87-201219450 'in a slurry state' at 25 ° C. 30 minutes. Thereafter, the reaction solution was filtered, and the solid was dried under reduced pressure at 70 ° C for 3 hours to obtain Compound 4 (yield: 48.7 g, 0.193 mol, yield: 96.5%). The structure of Compound 4 was confirmed by 1H-NMR analysis. !H-NMR ( CDC13 ) : δ 9.02 ( t, 1H, J = 2.4Hz, Ar-H ), 8.58 ( ms 2Ή, Ar-H ) , 6.54 ( dd, 1H, J=17.6, 1.2Hz, -CH = CH2 ) , 6.27-6.20 ( m, 1H, -CH = CH2 ) , 5.99 ( dd, 1H, J = 10.8Hz, 1.2Hz, -CH = CH2 ) , 5.40 ( s, 2H, Ar-CH2-〇) [化57] [PdCI2(CH3CN)2]

P(0-tolyl)3 K3PO4 &lt;Example 3 &gt; Compound 2 (25_3 g, 0.0702 mol), Compound 4 (21.1 g, 0.08 37 mol), palladium chloride acetonitrile complex (0.572 g, 2.21 mmol) a suspension of ginseng (p-tolyl)phosphine (1.28 g, 4.2 1 mmol), tripotassium phosphate (22.7 g, 0.107 mol), and dimethylacetamide 1 70 g at room temperature with a septum After the pressure was reduced to 50 T rr, the pressure was reversed 10 times with nitrogen to remove the oxygen contained in the reactor and dimethyl acetamide. Thereafter, the temperature was raised, and the mixture was stirred at 110 ° C for 3 hours in a nitrogen atmosphere. After completion of the reaction, the solvent was distilled off, and the mixture was extracted with 200 g of water and 25 g of chloroform -88-s 201219450. The aqueous layer which had been separated was further extracted twice with 250 g of chloroform, and the obtained organic layer was dried over anhydrous magnesium sulfate. Magnesium sulfate was obtained by filtration, and the obtained organic layer was evaporated under reduced pressure, and the obtained crude product was washed with acetonitrile (1 70 g). Thereafter, the crystals were filtered, and the obtained solid fraction was dried under reduced pressure to give Compound 5 (yield: 32.5 g, 〇 〇671 mol, yield: 95.6%). The structure of Compound 5 was confirmed by 1H-NMR analysis. ^-NMR (CDC13): δ 9.01 (t, 1H, Ar-H), 8.61 (d, 2H, J = 1.6 Hz, Ar-H), 7.74 (d, 1H, J = 16.0 Hz, -CH = CH -Ar ), 7.49 ( d, 2H, J = 7.6Hz, Ar-H) , 6.91 ( d, 2H, J = 7.6Hz, Ar-H) , 6.39 ( d, 1H, J=16.0Hz, -CH = CH-Ar) , 5.42 (s, 2H, Ar-CHz-O ) , 3.99 ( t, 2H, J = 6.4Hz, Ar-0-CH2 ), 1.83 - 1.76 (m, 2H, Ar-0-CH2- CH2-) , 1.4 9 - 1.2 8 ( m, 14H, Ar-〇- C H2 - C H2 - C 7 H 1 4 - ) , 0.89 ( t, 3H, J = 6.4Hz, -CH2-CH3 】

&lt;Example 4&gt; A solution of ammonium chloride (9.9 g, 0.185 mol) dissolved in 90.0 g of pure water was stirred and stirred to 5 5 °C. After reaching 5 5 °C, iron powder (5 1. 1 g, -89-201219450 0.915 mol) was placed, and the temperature was raised to 80 °C. After reaching 80 ° C, Compound 5 (29.0 g, 0_0599 mol) which had been dissolved in 145 g of toluene heated to 80 ° C was dropped. After the completion of the dropwise addition, the mixture was further stirred for 2 hours. After the completion of the reaction, hot filtration was carried out under the conditions of 8 (TC), and the obtained reaction liquid was separated to remove the aqueous layer. 1.2 g of activated carbon was placed therein. The obtained organic layer was stirred at 80 ° C for 30 minutes under heating, and then subjected to hot filtration under heating at 80 ° C, and the obtained organic layer was heated to 8 ° C in advance. The obtained organic layer was washed twice with anhydrous magnesium sulfate, and then magnesium sulfate was removed by filtration, and the obtained organic layer was evaporated under reduced pressure to give compound 6 (yield 18.7 g, 0.0440 mol) yield was 73.5%). The structure of Compound 6 was confirmed by 1 Η·Ν MR analysis. *H-NMR (CDC13): δ 7.67 (d, 1H, J = 16.0 Ηζ, - CH = CH-Ar), 7.45 (d, 2 Η, J = 8.4 Hz, Ar-H), 6.88 (d, 2H, J = 8.4Hz, Ar-H), 6.34 (d, 1H, J=16.0Hz, -CH = CH-Ar), 6.15 ( d, 2H, J=1.6Hz} Ar-H) , 5.98 ( t, 1H , J=1.6Hz, Ar-H) , 5.05 ( s, 2H, Ar-CH2-〇) , 3.97 ( t, 2H, J = 6.4Hz, Ar-0-CH2 ) , 3.62 ( b, 4H, NH2 ) , 1.82- 1.76 ( m, 2H, Ar-O-CH2-CH2- ) , 1.46- 1.27 ( m, 14H, Ar- 0- CH2-CH2-C7H , 4-), 0.88 ( t, 3H, J = 7.2 Hz, -CH2-CH3). 【化59】

-90- s 201219450 Tetrahydrofuran (281 g) of borane dimethyl sulfide complex (57.0 g, 750 mmol) was added dropwise to 2, 4-dinitrophenylacetic acid (56.6 g, 250 mmol) in tetrahydrofuran over 1 hour. (452 g) The solution was stirred at room temperature for 22 hours. Thereafter, water (1 1 2 g ) was added dropwise at 0 ° C for 2 hours, and stirred at room temperature for 2 hours, and then extracted with ethyl acetate and water, the aqueous layer was separated, and the organic layer was dried over magnesium sulfate. . The magnesium sulfate was removed by filtration, and the obtained organic layer was concentrated, and the obtained crude product was recrystallized from ethyl acetate and hexane to obtain 2,4-dinitrophenylethyl alcohol 1 (42.1 g, 79% yield). »H-NMR ( CDC13 ) : δ 8.79 ( d, 1H, J = 2.4 Hz, Ar-H ), 8.40 ( dd, 1H, J = 8.4, 2.4 Hz, Ar-H ) , 7.70 (d, 1H, J = 8.4Hz, Ar-H) , 4.01 ( dt, 2H, J = 5.2, 6.0 Hz, CH2-OH), 3.29 ( t, 2H, J = 6.0 Hz, Ar-CH2) , 1.63 ( t, 1H, J = 5.2 Hz, -OH). 【化60】

OH (W, K2C03&gt; jj^^, C4H9 1 2 dimethylformamide (90.1 g) was added to iodine butane (30.0 g, 1 63 mmol), 4-iodide; acid (3 9.4 g '1 7 9 mmol) and cesium carbonate (27.0 g, 196 mmol) were stirred at 85 ° C for 2 hours, after which potassium carbonate was removed by filtration, followed by extraction with toluene and 1 equivalent of aqueous sodium hydroxide. The layers were separated, and the obtained organic layer was dried over magnesium sulfate, and then filtered, and then evaporated to ethyl sulfate, and the organic layer was concentrated to afford -91 - 201219450 ether compound 2 (36-2 g, 81% yield). ( CDC13 ) : &lt;5 7.5 3 (

2h, J = 8.8 Hz, Ar-H ), 6.66 ( d, 2H, J = 8.8 Hz, Ar-jj) 5 3.90 ( t, 2H, J = 6.6

Hz, 0-CH2), 1.76 (m, 2H, O-CH 2, CH2,), 1.47 (m, 2H, CH2-CH3), 0.96 (t, 3H, J = 7.6 Uy, ... CH3). 【化61】

CH2=CHC02H, Bu3N, jjj^j^〇, C4H9 Pd(〇Ac)2, (o-tol)3P^2 Dimethylglyoxime (362g) was added to w8 in ether compound 2 (36.2g, 1 3 1 mmol ), acrylic acid (1 3.0 g, ! δ Λ 6 l8〇mm〇l ), palladium acetate (0.269 g, l_20 mmol), ginseng (p-tolyl) phosphine (〇73〇g, 2.40mmol) And tributylamine (67.9 g, 3 66_〇丨), and stirred at 14 ° C for 2 hours. Thereafter, extraction was carried out with ethyl acetate and water to separate the aqueous layer. The organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the obtained organic layer was concentrated to recrystallize the obtained crude product with ethyl acetate and hexane to obtain cinnamic acid derivative 3 (21.1 g, 73% yield). H-NMR ( DMSO ) : δ 12.2 ( s, 1 Η, C02H), 7.62 (d, 2H, J = 8.8 Hz, Ar-H), 7.54 (d, 1H, J = 16.0 Hz, CO-CH = CH) , 6.95 ( d, 2H, J = 8.8 Hz, Ar-H ), 6.36 ( d, 1H, J = 16.0 Hz, CO-CH = CH), 4.01 ( t' 2H, j = 6.6 Hz, 0-CH2) , 1_69 (m, 2H, 0-CH2-CH2), 1.44 (m, 2H, CH2-CH3), 0.93 (t, 3H, J = 7.4 Hz, -CH3). s -92- 201219450 【化62】

jOC&quot;. ' OaN^^N02 HOjC

My,·

EDC, C4H9 £MAP, c4h9 Oxidizing food of cassia, phenylethyl alcohol 1 ( 15.6 0.895 g ' 7.32mm〇l \ g 3 (1 6.2 g ' 7 3.5 mm ο 1 ), 73.5 mmol), and Methyl valerin was hydrolyzed in tetrahydrofuran (23 2g), propyl carbodiimide nitropyridine hydrochloride (1 - ethyl-3-(3-dimethylhydanol, 84.5 〇). After the addition, the aqueous layer was separated by ethyl acetate and water, and the organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the obtained organic layer was concentrated. The crude product was purified by column chromatography to give dinitro compound 4 (19.9 g, 65% yield). JH-NMR (CDClj): δ 8.83 (d, 1H, J = 2.4 Hz, Ar -H ), 8.40 ( dd, 1H, J = 8.8, 2.4 Hz, Ar-H ) , 7.66 ( d, 1H, J = 8.8 Hz, Ar-H), 7-60 ( d,1H, J=16.0 Hz ,CO-CH = CH) '7.46 ( d,2H,J = 8.4 Hz, Ar-H), 6.89 ( d,2H, J = 8.4 Hz, Ar- H ), 6.21 ( d, 1H, J=16.0 Hz , CO-CH = CH ) 4.53 (“ 2H, J = 6.4 Hz, CH2-〇C〇), 4.00 ( t, 2H, J = 6.6 Hz, C6H4-〇-CH2), 3 · 4 5 ( m,2 H,J = 6.4 H z,A r - CH 2 ),1 · 7 8 ( m,2 H,〇_ 鞠6.2g CH2-CH2 ) , 1.52 ( m, 2H, CH2- CH3) , 0.98 3H, 7.4 Hz, -CH3 ) -93- 201219450

Dinitro compound 4 (19.9 g, 48.0 mmol), reduced iron (32.2 g, 583 mmol), and ammonium chloride (15.4 g, 288 mmol) were dissolved in ethyl acetate (200 g) and water (77.1 g) to Stir at 70 ° C for 14 hours. After that, take 70. (: As it is, it is filtered using the sulphite, and the obtained filtrate is dried by magnesium sulfate. The magnesium sulfate is removed by filtration, and the obtained organic layer is concentrated to obtain a crude product. The obtained crude product is dissolved. To the tetrahydrofuran (200 g), activated carbon (2.00 g) was added, and the mixture was stirred at room temperature for 18 hours. The activated carbon was removed by filtration, and the organic layer was concentrated to give the desired compound diamine compound 5 (15.5 g, 91% yield). JH-NMR (CDC13): δ 7.65 (d, 1H, J = 16.0 Hz, CO-CH = CH), 7.4 1 (d, 2H, J = 8.4 Hz, Ar-H,), 6.89 (d, 2H, J = 8.4 Hz, Ar-H), 6.85 (d, 1H, J = 8 · 0 Hz, Ar-H), 6.30 (d, 1H, J = 16.0 Hz, CO-CH = CH), 6.10 ( Dd, 1H, J = 8.0, 2.4 Hz, Ar-H), 6.07 (d, 1H, J = 2.4 Hz Ar-H), 4.30 ( t, 2H, J = 7.6 Hz, CH2-OCO), 4.00 (t , 2H, J = 6.4 Hz, C6H4-0-CH2), 3.88 (br-s, 2H, NH2), 3.56 (br-s, 2H, NH2), 2.81 ( m, 2H, J = 7.6 Hz, Ar- CH2), 1.78 (m, 2H, 0-CH2-CH2), 1.49 (m, 2H, CH2-CH3), 0.98 (t, 3H, J = 7.2 Hz, -CH3). [Synthesis of polyglycine] -9 4- s 201219450 The following is a shorthand for the tetracarboxylic dianhydride and the diamine compound used in the synthesis of polylysine. (tetracarboxylic dianhydride) PMDA: pyromellitic dianhydride CBDA: 1, 2,3,4-cyclobutanetetracarboxylic dianhydride (diamine compound) p-PDA : P-phenylenediamine DA1: 3,5-diaminobenzyl 3-(4-(4-decyloxy) )phenyl)acrylate [64]

(Organic solvent) NMP: N-methyl-2-pyrrolidone BC : butyl cyanidin &lt; molecular weight determination of polyimine] The molecular weight of polyimine is saturated with a room temperature gel made by SSC A chromatography (GPC) apparatus (SSC-7200) and a column made by Shodex Co., Ltd.-95-201219450 (KD-803, KD-805) were measured as follows.

Column temperature: 50 °C Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide hydrate (LiBr · H20) is 30 mmol / L, phosphoric acid · anhydrous crystals (〇-phosphoric acid) 30 mmol/L and tetrahydrofuran (THF) were 10 ml/L. Flow rate: 1.0 ml of the standard sample for the production of the calibrated wire: TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories (molecular weight of about 12,000, 4,000 '1,000 ) 〇 &lt;Example 5 &gt; DAI (0.637 g, 1.50 mmol), and p-PDA (0.162 g, 1.50 mmol) were mixed in NMP (8.13 g) and stirred at room temperature 1 After dissolving in an hour, PMDA (0.63 5 g, 2.91 mmol) was added, and the reaction was allowed to proceed at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (9.56 g) and BC (4.78 g) were added to the polyamic acid solution (9.56 g), and 6 mass% of the liquid crystal alignment treatment agent (A) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 7,000 and a weight average molecular weight of 17,000. &lt;Example 6 &gt; DAI (〇.743g, 1.75mmol), and p-PDA (0.081g, 0.75mmol) were mixed in NMP (7.67g), and stirred at room temperature 1-96-

After S 201219450 was dissolved, PMDA (0.529 g, 2.43 mmol) was added, and the reaction was allowed to stand at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (9.22 g) and BC (4_51 g) were added to the polyamic acid solution (9_02 g), and 6 mass% of the liquid crystal alignment treatment agent (B) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 6,500 and a weight average molecular weight of 16,000. &lt;Example 7 &gt; DAI (〇.849g' 2.0 mmol) was mixed in NMP (7.11 g) and stirred at room temperature for 1 hour to dissolve, then PMDA (0.424 g ' 1.94 mmol) was added to the chamber. The reaction was allowed to proceed for 12 hours at room temperature to obtain a polyaminic acid solution. NMP (8.58 g) and BC (4.24 g) were added to the polyamic acid solution (8.48 g), and 6 mass% of the liquid crystal alignment treatment agent (C) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 6,000 and a weight average molecular weight of 16,000. &lt;Example 8 &gt; DA1 (0.509 g '1.20 mm ο 1 ), and p-PDA (0.194 g, 1.80 mmol) were mixed in NMP (7.22 g), and stirred at room temperature for 1 hour. After dissolving, CBDA (0.571 g, 2.91 mmol) was added, and the reaction was allowed to proceed for 12 hours at room temperature to obtain a polyaminic acid solution. N Μ P (9.0 2 g ) and BC (4.51 g) were added to the polyamic acid solution (9.02 g), and a 6 mass% liquid crystal alignment treatment agent (D) was obtained by stirring for 5 hours. -97- 201219450 The polyamino acid has a number average molecular weight of 8,000 and a weight average molecular weight of 21,000. &lt;Example 9 &gt; DA1 (0.6 3 7 g ' 1. 5 Ommo 1 ), and p-PD A (0.163 g, 1.5 0 mmol) were mixed in NMP (7.76 g), and stirred at room temperature 1 After dissolving for an hour, CBDA (0.571 g, 2.91 mmol) was added, and the reaction was allowed to proceed at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (9.1 3g) and BC (4.57g) were added to the polyamic acid solution (9.13g), and 6 mass% of the liquid crystal alignment treatment agent (E) was obtained by stirring for 5 hours. The average molecular weight was 7,000 and the weight average molecular weight was 19,000. &lt;Example 1&gt; Using the liquid crystal alignment treatment agent (A) obtained in Example 5, a liquid crystal cell was produced by a procedure as shown below. [Production of liquid crystal cell] The liquid crystal alignment agent (A) obtained in Example 5 was spin-coated on the ITO surface of a glass substrate to which a transparent electrode was adhered by an ITO film, and dried by a hot plate at 80 °C. After 90 seconds, the film was calcined in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. For this substrate, a linear polarized UV of 313 nm having an irradiation intensity of 8. 〇mW/cm 2 was irradiated with 100 mJ. The direction of the incident light, relative to the substrate normal -98-

S 201219450 is inclined 40β. The linear polarized UV is obtained by passing the ultraviolet light of the high pressure mercury lamp through a 313 nm band pass chopper, and preparing the above substrate by modulating the 313 nm polarizing plate, and spreading the film on the liquid crystal alignment film of the other substrate. After the glass bead spacer of m, the sealing agent is printed from above. Then, the liquid crystal alignment surfaces of the two substrates were opposed to each other, and the optical axis projection directions of the linearly polarized UVs for the respective substrates were pressed in antiparallel, and the sealing agent was thermally cured at 150 ° C for 105 minutes. A negative liquid crystal (manufactured by Merck, MLC-6608) was injected into the empty cell by a vacuum injection method to prepare a liquid crystal cell. Using the above method, the exposure amount of the irradiated polarized light UV was changed from OmJ to 1 000 mJ to produce the same liquid crystal cell. [Evaluation of liquid crystal cell] In the liquid crystal cell, the presence or absence of an abnormal region when a voltage of 8 V was applied and removed at 25 t was observed by a polarizing microscope, and the case of no abnormal region was evaluated as "good liquid crystal alignment". The liquid crystal cell produced as described above exhibited good vertical alignment in the absence of an applied voltage, and the liquid crystal alignment was also good when a voltage was applied. [Evaluation of Pretilt Angle] The pretilt angle of the liquid crystal cell was measured by the "AxoScan" manufactured by Axo Metrix Co., Ltd., by a Mueller matrix method. -99-201219450 &lt;Example 1 1> A liquid crystal cell was produced in the same manner as in Example 10 except that the liquid crystal alignment agent (A) was changed to the liquid crystal alignment agent (B), and the alignment of the liquid crystal was performed. And determination of the pretilt angle. <Example 1 2> A liquid crystal cell was produced in the same manner as in Example 10 except that the liquid crystal alignment agent (A) was changed to the liquid crystal alignment agent (C), and the alignment property of the liquid crystal and the pretilt angle were performed. Determination. &lt;Example 1 3&gt; A liquid crystal cell was produced in the same manner as in Example 10 except that the liquid crystal alignment agent (A) was changed to the liquid crystal alignment agent (D), and the alignment property and pretilt angle of the liquid crystal were performed. Determination. <Example 1 4> A liquid crystal cell was produced in the same manner as in Example 10 except that the liquid crystal alignment agent (A) was changed to the liquid crystal alignment agent (E), and the alignment property of the liquid crystal and the pretilt angle were performed. Determination. The composition ratios of the acid dianhydride and the diamine compound used in the production of the liquid crystal alignment agents (A) to (E) are shown in Table 1. In Table 1, the % in () is shown as the content ratio of the acid dianhydride or the diamine compound in the peracid dianhydride component or the total diamine component (mole. -100-201219450, further, in each example The pretilt angle of the manufactured liquid crystal cell was as shown in Table 2. [Table 1] Example Liquid crystal alignment treatment agent Acid dianhydride (mol%) Diamine compound (mol%) PMDA CBDA DA1 p-PDA 10 A 97 A 50 50 11 B 97 — 70 30 12 C 97 a 100 — 13 D a 97 40 60 14 E — 97 50 50 -101 - 201219450 [Table 2] Example liquid crystal alignment treatment agent uv irradiation amount 'liquid crystal alignment pretilt angle Voltage is not applied (Inca) When voltage is applied (Inca) 10 A Om J Good bad 9 0° 1 0 Om J Good 8 8. 8° 3 0 Om J Good 8 8. 7° 5 0 0 m J Good and good 8 8. 8° 1 0 0 OmJ Good 8 8. 8° 11 B Om J Good bad 9 0° 1 0 Om J Good good 8 9. 0° 3 0 0 m J Good good 8 9. 0° 5 0 0 m J m- good 8 9. 0° 1 0 0 OmJ good and good 8 9. 1° 12 C Om J m bad 9 0° 1 0 Om J good good 8 9. 2° 3 0 0 m J good 8 9. 1° 5 0 0 m J Good good 8 9. 2° 1 0 0 OmJ Good good 8 9. 2° 13 D Om J m- Poor 9 0° 1 0 Om J m- Good 8 8. 6° 3 0 Om J Goodness 8 8. 7° 5 0 Om J Cake good 8 8. 5° 10 0 OmJ m- Good 8 8. 9° 14 E 0 m J Good bad 9 0° 1 0 Om J Good good 8 8. 9° 3 0 Om J Good Good 8 8. 8° 5 0 Om J Good and good 8 8. 6° 10 0 OmJ Good and good 88. 8° From the results of Table 2, it was confirmed that the liquid crystal display element obtained by using the novel diamine compound of the present invention exhibited A good vertical alignment property is obtained, and by irradiating the polarized ultraviolet rays, even a so-called small amount of irradiation of 100 m J can confirm that the liquid crystal alignment exhibits a large pretilt angle. Further, by using the liquid crystal alignment film of the novel diamine compound of the present invention, it was confirmed that the pretilt angle can be kept constant irrespective of the irradiation amount of any ultraviolet rays. Therefore, it is indicated that the pre-tilt angle can be maintained in the stability of 201219450 even after being exposed to light such as a backlight for a long period of time. Therefore, the novel diamine compound of the present invention can be used for liquid crystal display elements for vertical alignment. The alignment film can also be used in a photo-alignment method in which liquid crystal alignment energy is imparted by ultraviolet irradiation. &lt;Comparative Example 1 &gt;C; 65]

Mix l.llg ( 2.70 mmol) of DA2 and o.llg (〇.3〇mmol) of DA3 in NMP (10.22g) and stir at room temperature! In the case of dissolution, the mixture was dissolved and added to 匚8〇8 0.58 § (2.94111111〇1), and the reaction was allowed to proceed for 12 hours at room temperature to obtain a polyaminic acid solution. NMP (9.0 g) and BC (9.0 g) were added to the polyamic acid solution (12.0 g), and a 6 mass% liquid crystal alignment treatment agent (F) was obtained by stirring for 5 hours. The polyamino acid had an average molecular weight of 12,000 and a weight average molecular weight of 29,000. In the above-described Example 10, a liquid crystal cell was produced in the same manner as in Example 10 except that the liquid crystal alignment agent (A) was changed to the liquid crystal alignment agent (F), and the alignment of the liquid crystal and the pretilt angle were performed. Determination. The composition ratios of the acid dianhydride -103 - 201219450 and the diamine compound used in the synthesis of the liquid crystal alignment agent (F) are shown in Table 3. Further, the pretilt angle of the liquid crystal cell produced in Comparative Example 1 is shown in Table 4. [Table 3] Example Liquid crystal alignment agent acid dianhydride (mol%) Diamine (mol%) PMDA CBDA DA1 DA2 DA3 p-PDA Comparative Example 1 F 99 90 10 [Table 4] Example Liquid crystal alignment agent UV irradiation The amount of liquid crystal 酉B to the pre-tilt voltage of the agent is not applied (increase) when the voltage is applied (imprinted), the comparison is F FJJ good bad 90° lOOmJ good bad 90° 300mJ good good 89.7° 500mJ good good 89.3. lOOOmJ Good Good 89.1. [Industrial Applicability] The liquid crystal display element having the liquid crystal alignment film obtained by the novel diamine compound of the present invention can maintain stability even when exposed to light such as a backlight for a long period of time, and is excellent in reliability. It can be suitably used for large-screen 'high-definition LCD TVs, etc. The entire disclosure of the specification, the scope of the patent application, and the abstract of Japanese Patent Application No. 2010-153075, filed on Jul. 5, 2011, the entire disclosure of which is incorporated herein by reference. -104-

Claims (1)

201219450 VII. Patent application scope: 1. A liquid crystal alignment treatment agent characterized in that it is selected from the group consisting of polylysine and polyamidene obtained by imidating the polyamidinate. a polymer obtained by reacting a diamine component having a diamine compound of the following formula [1] with a tetracarboxylic dianhydride component; wherein the polyamic acid is obtained by reacting a diamine component having a diamine compound of the following formula [1]; (wherein X1 is represented by a single bond, -CH20., -〇-, -COO-, -OCO-, -NHCO-, or -CONH-, and X2 is represented by an alkylene group having a carbon number of 1 to 3, and X3 is shown. For - 〇-, -NH-, or -NCR1) -, X4 is shown as a single bond, -〇-, -S-, or -NH-, X5 is shown as a single bond or by the following formula [χ5_ι]~[χ5 -5] selected carbocyclic ring, X6 is shown as a linear or branched alkyl group having a carbon number of 1 to 18, and X7 is represented by a hydrogen atom, -R2, -OR3, -NHR4, -N(R5)2 Or -SR6, where R1 to R6 are each independently shown as an alkyl group having 1 to 5 carbon atoms, and η is an integer of 1 or 2), [X2-!] [Xs-2] [XS-5] (However, in the above carbocyclic structure, any hydrogen atom may be replaced by ch3). 2. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the content of the diamine compound of the formula [1] in the above-mentioned diamine component is from -100 to 100% by mole. 3. The liquid crystal alignment treatment agent according to the first or second aspect of the invention, wherein X3 of the above formula [1] is a hydrogen atom. 4. The liquid crystal alignment treatment agent according to any one of the above claims, wherein X5 of the above formula [1] is a single bond. The liquid crystal alignment treatment agent according to any one of claims 1 to 4, wherein X1 of the above formula [1] is a single bond 'χ4 is -〇_° 6. As in the patent application range 1-5 The liquid crystal alignment treatment agent according to any one of the preceding claims, wherein the η of the above formula [1] is 1. 7. The liquid crystal alignment treatment agent according to any one of the above formulas, wherein X2 of the above formula [1] is -CH2-' X6 is an alkyl group having 8 to 12 carbon atoms. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above claims. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 7, which imparts liquid crystal alignment energy by irradiation of polarized or non-polarized radiation. A liquid crystal display element comprising a liquid crystal alignment film as claimed in claim 8 or 9. 11. A diamine compound represented by the following formula [1], [Chemical 3] -106- H2Njj h2n s 201219450 (wherein X1 is shown as a single bond, -CH20-, -〇-, -COO-, -OCO-, -NHCO-, or -CONH·, X2 is shown as carbon number 1~3 The alkyl group 'X3 is shown as -0_, _NH-, or -NCR1) _, X4 is shown as a single bond, -〇_, -S-, or ·NH-, and X5 is shown as a single bond or by the following formula [ a carbocyclic ring selected from the group of X5-l]~[X5-5], X6 is shown as a linear or branched alkyl group having a carbon number of 1 to 18', and is represented by a hydrogen atom, -R2, -OR3, -NHR4 , -Ν ( R5 ) 2, or _sr6, where R1 to R6 are independently shown as the base of the carbon number 1 to 5, and η is not an integer of 1 or 2), [Chemical 4] [XS-1] [XS-2J [X5-S] (However, in the above carbocyclic structure, any hydrogen atom may be substituted by CH3). The diamine compound according to the first aspect of the invention, wherein X3 of the above formula [1] is -〇-, and X7 is a hydrogen atom. A diamine compound according to claim 11 or 12, wherein X5 of the above formula [1] is a single bond. 14. The diamine compound as claimed in any of claims 11 to 13 wherein X1 of the above formula [1] is a single bond, and X4 is _〇-1, as described in the scope of application ii~1 4 In the above-mentioned formula, the η of the formula [1] is 1. 1 6 - The diamine compound of any one of the claims 1 to 15 wherein 'X' of the above formula [1] is -CH2., and Χ6 is an alkyl group having 8 to 12 carbon atoms. ».. -107- 201219450 1 7. A polyimine which reacts a diamine component containing a diamine compound according to any one of claims 1-6 to a tetracarboxylic dianhydride component. The obtained polyaminic acid or the obtained polyphosphonium amide is imidized. -108 S 201219450 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure··5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none