TW201206996A - Liquid crystal aligning agent, and liquid crystal display element using same - Google Patents

Abstract

Provided is a liquid crystal aligning agent which can form a liquid crystal alignment film for optical alignment enabling uniform liquid crystal alignment at an angle slightly tilted from the vertical. The liquid crystal aligning agent is characterised in having at least one type of polymer selected from a group comprising: polyamic acids obtained by subjecting a diamine component containing a diamine represented by formula [1] and a tetracarboxylic acid dianhydride component to a polymerisation reaction; and polyimides obtained by the cyclodehydration of said polyamic acids. (In formula [1], S represents a hydrogen atom, -CN, -O(CH2)mCH3, -(CH2)mCH3 (where m is an integer of 0-4), -NR1R2- (where R1 and R2 independently represent a hydrogen atom or a C1-6 alkyl group), a halogen atom, or a carboxyl group. P represents a single bond, a phenyl group, or a cyclohexyl group. Q represents a single bond, or a -O-, -COO- bonding group. R represents a C4-20 alkyl group.)

Description

201206996 VI. [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal display TfC element having the liquid crystal alignment film, and is suitable for And other novel diamines. [Prior Art] Liquid crystal display elements used in liquid crystal displays, such as LCD TVs, liquid crystal screens, and mobile devices, are excellent in productivity, and are excellent in chemical properties and thermal durability. The membrane is used at the most. A polyimine-based liquid crystal alignment film obtained by applying a solution of polyacrylic acid or polyimine to a substrate, and drying and calcining to obtain a polyimide film, and then applying it as needed Made by the alignment process. As a method of alignment treatment of a polyimide film, rubbing is most known, but recently, in a photoalignment method by polarized ultraviolet light, various polyimine-based liquid crystal alignment films are also available. Proposed. (Patent Document 1 to Patent Document 5) [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Publication No. 2001-517719 (Patent Document 2) Japanese Patent Publication No. 2003-520578 (Patent Document 3) [Patent Document 4] JP-A-2009-37104 [Patent Document 5] Japanese Patent Application Publication No. 2009-520702 [Patent Document] [Problems to be Solved by the Invention] Provided is a liquid crystal alignment film obtained by uniformly providing a liquid alignment type polyimine liquid crystal alignment agent which is vertically aligned in a state of only tilting, and a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal having the liquid crystal alignment film. A display element, and a novel diamine used in the raw material of the above liquid crystal alignment agent. [Means for Solving the Problems] The present invention has the following gist. A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of polylysine and polyamidene obtained by dehydration of the polyglycolic acid; wherein the polymerization The proline is obtained by polymerizing a diamine component represented by the following formula [2] containing a diamine represented by the following formula [1] with a tetracarboxylic dianhydride component represented by the following formula [3]. ; [Chemical 1]

[1] (In the formula), s is a hydrogen atom, -CN, -0(CH2)mCH3, -(CH2)mCH3 201206996 (m is an integer of 0 to 4), -NWR2- (R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a halogen atom or a carboxyl group. P is a single bond, a phenyl group or a cyclohexyl group. Q is a single bond or a bond group of -Ο-, -COO-. An alkyl group having a carbon number of 4 to 20); [Chemical 2] H2N-B-NH2 [ 2 ] (B in the formula [2] is a divalent organic group); [Chemical 3] Q 〇

(A) The liquid crystal alignment agent of the above formula (2), wherein the diamine component represented by the above formula [2] contains the above formula [1]. The diamine is 30 to 100 mol%. 3. The liquid crystal alignment agent according to the above 1 or 2, wherein the diamine represented by the above formula [1] is represented by the following formula [5], [Chemical 4]

In the formula (R), R is an alkyl group having a carbon number of 6 to 20). 201206996 4. A liquid crystal alignment film obtained by coating and calcining a liquid crystal alignment agent according to any one of the above 1 to 3. A liquid crystal display element having a liquid crystal alignment film as described above, wherein the type of diamine is represented by the following formula [1].

(In the formula [1], S is a hydrogen atom, -CN, -0(CH2)mCH3, -(CH2)mCH3 (m is an integer of 0 to 4), -NWR2- (R1, R2 are each independently a hydrogen atom or A C 1 to 6 alkyl group, a halogen atom or a carboxyl group. P is a single bond, a phenyl group or a cyclohexyl group. Q is a single bond or a bond group of -0-, -coo-. R is a carbon number 4 to 20 alkyl groups). 7. The above-mentioned 6-diamine, wherein the diamine represented by the above formula [1] is represented by the following formula [5].

(In the formula [1], R is a hospital base having a carbon number of 6 to 20).

8. The above-mentioned 6-diamine, wherein the diamine represented by the above formula is (E -8 - 201206996 )-3,5-diaminobenzyl·3-( 2_dodeyl-13·2) Side oxyisoporphyrin-5-yl)acrylate, (E)-3,5-diaminobenzyl-3-(2-indolyl-1,3-di-isoxisoisoporphyrin-5- Acrylate, or (E) -3,5-diaminobenzyl-3-(2-octyl-1,3-dioxaisoindoline-5-yl) acrylate, (E) -3,5-diaminobenzyl-3-(2-(4-butoxyphenyl)-1,3-dioxaisoindoline-5-yl)acrylate, (E)-3 , 5-diaminobenzyl-3-(2-mercapto-1,3-dioxaisoindoline-4-yl)propionate, or (E)-3,5-diamino Benzyl-3-(2-mercapto-6-methoxy-1,3-di-isoxisoindoline-5-yl)acrylate. A polyamine acid which is a diamine component represented by the following formula [2] containing a diamine according to any one of the above 6 to 8 and a tetracarboxylic dianhydride represented by the following formula [3] By component polymerization, [Chem. 7] H2N-B NH2 [ 2 ] (B in the formula [2] is a divalent organic group) '[8]

[3] (A in the formula [3] is a tetravalent organic group) ° 1 〇. - Polyimine imine" is obtained by the above-mentioned 9 polyamines dehydration ring closure β 201206996 [Effect of the invention The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has a good vertical alignment with respect to the film surface liquid crystal when the alignment treatment is not performed. Further, by performing the photoalignment treatment on the liquid crystal alignment film, the alignment of the liquid crystal in a state of being vertically inclined only can be uniformly obtained. Further, according to the present invention, it is possible to provide a novel diamine which is a raw material which is a polyamic acid or a polyimine in a liquid crystal alignment agent or the like. [Best Mode of the Invention] <Diamine of the Invention> The raw material of the liquid crystal alignment agent of the present invention is a diamine represented by the following formula [1] (hereinafter, also referred to as the second invention) amine). [Chemistry 9]

(In the formula [1], S is a hydrogen atom, -CN, -CKCHOmCHs, -(CH2)mCH3 (m is an integer of 0 to 4)' -NWR2- (R1, R2 are each independently a hydrogen atom or a carbon number of 1~) 6 alkyl), a halogen atom, or a carboxyl group. P is a single bond, a phenyl group or a cyclohexyl group. Q is a single bond, or a bond group of -〇-, -COO-. R is a carbon number of 4-20 alkyl). The diamine represented by the formula [II] of the present invention can be expressed as a compound having a specific substituent on the skeleton of diamine benzene (phenylenediamine). At this time, -10- 201206996 'the position of the two amine groups of the skeleton of the diamine benzene is not particularly limited. To exemplify the specific example, 'When the position of a specific substituent is set to the nick position, it is 2,3-diamine benzene, 2,4-diamine benzene, 2,5-diamine benzene, 2,6- Diamine benzene, 3,4-diamine benzene, and 3,5-diamine benzene. Among them, from the viewpoint of reactivity with tetracarboxylic dianhydride, g is preferably 2,4-aminobenzene or 3,5-diamine benzene. In the diamine represented by the formula [1], R is an alkyl group having 4 to 20 carbon atoms. The alkyl group may be linear or may have a branched structure. The diamine of which the carbon number of the alkyl group is larger, the liquid crystal alignment film thus obtained, the higher the ability of the liquid crystal to stand vertically. On the other hand, if the ability to vertically stand the liquid crystal is increased, the amount of vertical tilt of the liquid crystal during photoalignment processing becomes small. Therefore, the carbon number of the alkyl group of 'R is selected from the balance of the two, preferably 6 to 16 and more preferably 8 to 12. Further, in the formula [1], it is preferable that S is a hydrogen atom, -CH3, or -〇ch3 is preferably 'p is a single bond, a phenyl group, or a cyclohexyl group, or q is a carbon number of 4~ 1 2 is better. Among the diamines of the present invention, a diamine represented by the following formula [5] can be exemplified as a preferred specific example. [化10]

<Synthesis method of diamine of the present invention> -11 - 201206996 The diamine of the present invention can be obtained by reducing a nitro group of a dinitro compound represented by the following formula [4]. S, S, R, P, Q, and R in the formula [4] have the same definitions as those of the formula [1]. [11]

The reduction of the dinitro compound of the formula [4] is carried out by selecting a reaction condition which does not impair the double bond of the side chain. For this reason, it is preferred to use a metal such as Fe, Sn or Zn or a salt of such a metal together with a proton source. The above metal or metal salt may be used alone or in 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. As long as the solvent can withstand the environment under a reducing atmosphere, dimethylformamide (DMF), dimethyl hydrazine (DMSO), dimethylacetamide (DMAc), N-methyl can be used. Aprotic polar organic solvent such as pyrrolidone (NMP), diethyl ether (Et20) 'diisopropyl ether (i-Pr20), tert-butyl methyl ether (TBME), cyclopentyl methyl ether ( CPME), ethers such as tetrahydrofuran (THF) and dioxane, aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, benzene, toluene, xylene, mesitylene, chlorobenzene, dichloro An aromatic hydrocarbon such as benzene, nitrobenzene or tetrahydronaphthalene; a lower fatty acid ester such as methyl acetate, ethyl acetate, butyl acetate or methyl propionate; or a nitrile such as acetonitrile, propionitrile or butyronitrile. . These solvents can be appropriately selected in consideration of the reaction conditions, the easiness of the reaction, and the like, and are preferably selected from the group consisting of one or two or more kinds of the above-mentioned solvents. Further, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is in the range of from -100 °C to the boiling point of the solvent to be used, preferably in the range of from -50 to 150 °C. The reaction time is from 0.1 to 1,000 hours. The obtained diamine of the formula [1] can be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. The dinitro compound of the above formula [4], in the coexistence of the compound [5] and the compound [6] in the presence of a metal complex catalyst, a ligand and a base, can be carried out by a Heck reaction or the like. It is obtained by coupling reaction. [化12]

X' in the compound [5] may be any functional group having a dissociation ability. For example, a halogen such as F'Cl' Br, I or the like, or a tosylate (· 0S02C6H4-p-CH3), methane sulfonate may be used. a sulfonate such as an ester (-〇S02CH3) or a trifluoromethanesulfonate (X = -0S02CF3). When considering the reactivity, it is preferred to use Br, I or trifluoromethanesulfonate. As the above metal complex, a palladium complex or a nickel complex is used. As the above catalyst, various types can be used, but a so-called low valence IG complex or an anomaly complex is preferable, and in particular, a secondary or tertiary sub-pity acid is used as a ligand. A zero-valent complex is preferred. Further, in the reaction system, it is also possible to use a precursor which can be easily converted into a zero-valent complex. In the reaction system, -13-201206996 can also be used as a ligand which does not contain a tertiary phosphine or a tertiary A complex of phosphoric acid, mixed with a tertiary phosphine or a tertiary phosphite, produces a low valence complex which uses a tertiary phosphine or a tertiary phosphite as a ligand. Examples of the tertiary phosphine or tertiary phosphorous acid as a ligand include, for example, triphenylphosphine, tris-fluorenyltolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2- Bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, l,i'-bis(diphenyl As the phosphino group, ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, etc., two or more complex compounds containing such a ligand may be suitably used. As the catalyst, it is also preferred to use 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, in combination with the above ligand. . 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) ) palladium dichloride, bis(benzonitrile) dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, etc.; further, as a complex which already contains a tertiary phosphine or a tertiary phosphite as a ligand For example, dimethylbis(triphenylphosphine)palladium, dimethylbis(diphenylmethylphosphine)palladium, (ethylene)bis(triphenylphosphine)palladium, ruthenium (triphenylphosphine)palladium , bis(triphenylphosphine) dichloropalladium or the like. The amount of the palladium complex to be used may be a so-called catalyst amount, and is usually 20 mol% or less, preferably 10 mol% or less, based on the substrate. As the above base, in addition to inorganic base or methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine-14-201206996, three Propylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, Other than the amines such as Colin base, sodium acetate, potassium acetate, lithium acetate or the like can also be used. As the solvent, it is preferred to be stable under the reaction conditions and to be inert without hindering the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et20, i-Pr2, TBME, CPME, THF, dioxane, etc.) can be used. , monthly aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, four Hydrogen naphthalene, 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. These solvents may be used alone or in combination of two or more. Further, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is preferably from -100 ° C to the boiling point of the solvent used, and is preferably from -50 to 150. (The range of: The reaction time is 0.1 to 1,000 hours. The obtained dinitro compound of the formula [4] can be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. [5] A phthalic anhydride having a functional group X as described below can be reacted with a primary amine compound to form a proline acid, and then dehydrated and closed. -15- 201206996

In order to obtain the above proline, it is obtained by reacting phthalic anhydride with a primary amine compound in a solvent which does not react with an acid anhydride or an amine of a substrate. When acetic anhydride or propionic anhydride is allowed to act on the obtained valine acid, a dehydration ring closure occurs, and the compound [5] can be obtained. The solvent' is preferably one which is stable under the reaction conditions and inert and does not interfere with the reaction. For example, an aprotic polar organic solvent (DMF, DMSO, DMAc, NMP, etc.), an acid (Et2〇, i-Pr20, TBME, CPME 'THF 'dioxane, etc.), an aliphatic hydrocarbon (pentane) may be mentioned. , hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen-based hydrocarbons ( Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, Nitrile, etc.), organic acids such as formic acid, acetic acid, and propionic acid. These solvents can be selected in consideration of the reaction conditions, the ease of production, and the like. In this case, the above solvents may be used alone or in combination of two or more. Further, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. As the reaction accelerator, pyridine or N,N-dimethylaminopyridine or N-methylmorpholine can be used. The reaction temperature is from -100 ° C to the boiling point of the solvent to be used, preferably from -50 to 150 ° C. The reaction time is from 0.1 to 1,000 hours. The obtained compound [5] can be purified by recrystallization, distillation, hydrazine gel column -16-201206996 chromatography, activated carbon or the like. Further, the compound [5] can also be obtained by subjecting an phthalimine compound having a functional group X to alkylation of a quinone imine moiety, as described below. At this time, X1 of the alkylating agent can be exemplified as the same as the functional group X of the compound [5]. X and X1 may also be the same functional groups. [Chem. 14]

The above reaction is carried out in the presence of a base. As the base, an inorganic base or an amine such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid planing, NaH or KH can be used. Or an organic base such as t-BuONa or t-BuOK. Further, an organic lithium reagent such as η-butyllithium, sec-butyllithium or t-butyllithium, a methylprene reagent, an ethylgepine reagent, or the like may be used. Propyl decylamine (LDA), lithium hexamethyldiazepine (LiHMDS), sodium hexamethyldisodium sulphate (NaHMDS), potassium hexamethyldioxane (KHMDS), sodium amination (NaNH2) And amidoxime such as potassium azide (KNH2). As the solvent, it is preferred to be stable under the reaction conditions and inert to prevent the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), acids (Et20, i-Pr2〇, TBME, CPME, THF, two π ox, etc.) can be used. 'Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene-17-201206996 , tetrahydronaphthalene, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, propionate Ester, etc., nitrile (acetonitrile, propionitrile, butyronitrile, etc.) 0 These solvents can be selected in consideration of the reaction conditions or the ease of reaction, etc. In this case, the above solvents may be used alone or in combination 2 More than one kind. Further, an appropriate dehydrating agent or desiccant may be used as the nonaqueous solvent, as the case may be. The reaction temperature is in the range of from -1 00 t to the boiling point of the solvent to be used, preferably from -50 to 150 °C. The reaction time is from 0.1 to 1,000 hours. The obtained compound [5] can be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. The above compound [6] is produced by esterification between the corresponding dinitrobenzyl alcohol and an acrylic acid derivative. As the acrylic acid derivative, an acid halide such as an acrylic acid chloride or an acrylic acid bromide or an acrylic anhydride is preferably used. In this case, as the base, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid, NaH or KaH can be used. , an amine or an organic base such as t-BuONa or t-BuOK. Further, the compound [6] may be subjected to transesterification of an acrylate such as methyl acrylate or ethyl acrylate with dinitrobenzyl alcohol, or acrylonitrile with dinitrobenzyl chloride or dinitrobromination. The reaction of a dinitrobenzyl halide such as a benzyl group is carried out. The dinitro compound of the formula [4] can also be obtained by reacting the compound [7] with the compound [8] as follows. -18- 201206996 [化15]

Y of the compound [8] is a functional group reactive with a carboxyl group, and examples thereof include a hydroxyl group, a fluorine, a chlorine, a bromine, a halogen of iodine, a methanesulfonate, a mercaptosulfonate, a besylate, a tosylate. Such as sulfonate esters and the like. When hydrazine is a hydroxyl group, the compound [7] is directly reacted with the compound [8] in the presence of a mineral acid or a Lewis acid catalyst to obtain a dinitro compound [4]. In this case, for example, dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), carbonyldiimidazole (CDI) is used. The condensing agent can promote the reaction efficiently. Further, when hydrazine is a hydroxy group, SOC12 or SOBr2 or the like is allowed to act on the carboxyl group of the compound [7] to be converted into a corresponding acid halide, and it is effective to react with the compound [8] in the presence of a base. When Y is a halogen or a sulfonate, the compound [7] is reacted with the compound [8] in the presence of a base. As the base, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate or trimethylamine or the like can be used. Amines such as ethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, Colin base, and the like. The solvent used in the reaction of the compound [7] with the compound [8] is preferably one which is stable under the reaction conditions and inert, and does not interfere with the reaction. For example, -19-201206996, for example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et20, i-Pr20, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons Classes (pentane, hexane, heptane 'petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen It is a hydrocarbon (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.). These solvents can be selected in consideration of the reaction conditions, the ease of production, and the like. In this case, the above solvents may be used alone or in combination of two or more. Further, an appropriate dehydrating agent or desiccant may be used as the nonaqueous solvent, as the case may be. The reaction temperature is in the range of -10 (TC to the boiling point of the solvent to be used, preferably -50 to 150 ° C. The reaction time is 0.1 to 1,000 hours. The dinitro compound of the obtained compound [4] It can be purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon, etc. 尙, Y is a halogen or sulfonate compound [8], which can be made from a compound in which Y is a hydroxyl group [8]. For example, using a halogenating agent such as BBr3, BC13, PBr3, PC13, PPh3-CBr4 'PPh3-CC14 'PPh3-I2, SOBr2, SOCl2, etc., a compound in which Y is a halogen [8] can be produced. Further, Y is a hydroxyl group. The compound [8] is reacted with a sulfonic acid halide in the presence of a base to convert it into a sulfonate such as a methanesulfonate or a tosylate. The sulfonate is further substituted with Nal, NaBr, and NaCl. The reaction of a halogen-containing salt such as KI, KBr, KC1, Lil, LiBr or LiCl can also be converted into a compound in which Y is a halogen [8]. The compound [7] can be obtained from the above compound [5] as follows. -20- 201206996 [Chem. 16]

The reaction of the compound [5] with the compound [9] can be carried out by the same reaction as the above reaction of obtaining the dinitro compound [4] from the compound [5] and the compound [6]. Y2 of the compound [9] is a linear alkyl group such as a methyl group, an ethyl group or a benzyl group; a branched alkyl group such as an isopropyl group; a cyclic alkyl group such as cyclohexane; or an aromatic group such as a phenyl group or a tolyl group; Base. Further, a protecting group capable of withstanding the reaction conditions can also be used. For example, an acetal protecting group such as a methoxymethyl group, an ethoxyethyl group, a tetrahydropentanyl group or a tetrahydrofuranyl group, a trimethylsulfonyl group, a triethylsulfonyl group, or a tris(isopropyl group). A mercapto protecting group such as a mercapto group, a triphenylsulfonyl group, a tert-butyldimethylhydrazine group, a tert-butyldiphenylfluorenyl group, an isophenylpropyldiphenylfluorenyl group or the like. When considering the resistance to the reaction conditions, a methyl group, an ethyl group, a benzyl group, a triethylsulfonyl group or a tetrahydropyranyl group is preferred. The methyl group, the ethyl group or the benzyl group is particularly preferred from the viewpoint of the availability of the starting material or the reactivity of the next step. The compound [10] obtained above can be converted into the compound [7] by hydrolysis. Hydrolysis can be carried out acidic or alkaline. As the acid, an organic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as formic acid, acetic acid or toluenesulfonic acid can be used, and the amount thereof is 20 mol% or less, usually 10 mol% or less, based on the substrate. In the case of acid hydrolysis, it is preferred to carry out the reaction by allowing an excess amount of water to coexist. -21 - 201206996. As the base, it is generally preferred to use an inorganic substance such as NaOH, KOH or LiOH as an aqueous solution. The amount used is such that the reaction is carried out smoothly with respect to the use of the substrate in an equivalent amount or more. As the solvent, it is preferred to be stable under the reaction conditions and inert to prevent the reaction. Water, alcohols, amines, ethers (Et20, i-Pr20, TBME, CPME, THF, 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, two Ethyl chloride, etc.). These solvents can be selected in consideration of the reaction conditions, the ease of production, and the like. In this case, the above solvents may be used alone or in combination of two or more. Further, a dehydrating agent or a desiccant may be used as the nonaqueous solvent. The reaction temperature is in the range of from -10 ° C to the boiling point of the solvent used, preferably from -50 to 150 ° C. The reaction time is from 0.1 to 1,000 hours. The obtained compound [7] is preferably purified by recrystallization, distillation, hydrazine gel column chromatography, activated carbon or the like. Further, the compound [10] can also be converted into a compound [7] by a transesterification reaction. In this case, the use of an acid such as sulfuric acid in a catalytic amount can be achieved by reacting excess formic acid or acetic acid. <Polyuric acid> The polylysine used in the liquid crystal alignment agent of the present invention is represented by the following formula [2] containing the diamine of the present invention represented by the above formula [1] The amine component is poly-22-201206996 proline which is obtained by polymerizing a tetracarboxylic dianhydride component represented by the following formula [3]. H2N-B-NH2 [2] (B in the formula [2] is a divalent organic group). [Chem. 18] Q Ο VAV [3] Ο 〇 (The enthalpy in the formula [3] is a tetravalent organic group). The diamine component represented by the formula [2] used in the polymerization reaction of poly-proline may be one type of diamine or two or more types of diamine. The tetracarboxylic dianhydride component represented by the formula [3] may be one type of tetracarboxylic dianhydride or two or more kinds of tetracarboxylic dianhydride. The ratio of the diamine of the present invention used in the diamine component of the formula [2] used in the polymerization of polyproline is not particularly limited. The preferred ratio of use of the diamine of the present invention is 10% by mole or more, preferably 20% by mole or more, and more preferably 30% by mole or more based on the entire diamine component. The 100% by mole of the diamine component may be a diamine represented by the formula [1]. When the ratio of use of the diamine represented by the formula [1] is larger, the ability to vertically stand the liquid crystal becomes higher as the liquid crystal alignment film, and the efficiency of the photoalignment treatment is increased. In the diamine component represented by the formula [2] used in the polymerization of polyproline, the ratio of use of the diamine of the present invention is less than 1 〇〇mol·>/. In the case of the other diamine contained in the diamine component, it is not particularly limited. As such a diamine of -23-201206996, a diamine known as a raw material of polylysine can be used. Specific examples of the other diamines described above include, for example, B in the above formula [2] as a divalent organic diamine represented by B-1 to B-104 in the following Tables 1 to 5. These diamines may be used alone or in combination of two or more. -24- 201206996 [Table 1] Β·1 B-2 XX B-3 /OXX Β-4 Β·5 ,χπχ3 B-6 Β·7 Pu B-8 iX B-9 j〇C ΒΊΟ O-CHs B -ll 众' B-12 h3c >-ch3 Β·13 ^V^COOH B*14 V^rwCOOH uC B.15 CXX)H Β_16 ch3 X^CH3 Β-Γ7 j〇C B_18 Cl Β-19 Good cf Ch3 B-20 B-21 Β-22 B-23 XT B-24 Β-25 B-26 t- B-27 & Β·28 ^rQr B-29 H3C CH3 B-30 PH3 h3c -25- 201206996 [ Table 2]

B-31 f3c Β·32 jxa Β·33 χτα Β·34 Β·35 Β·36 χΛα Β·37 Β-38 Xrbk Β-39 ^oky Β-40 HaC CH3 Β-41 F3C cf3 ιΛχ Β·42 ^3CyCF3 Β-43 Η人Β-44 -φ〇Γ Β·45 Β-46 Β·47 Β·48 Β-49 Β-50 q_^b Β-δ1 -Qr^Qr Β-52 V Β·53 Β·54 iX -26- 201206996 [Table 3] Β·55 B-56 Β-57 CH3 B-58 ja°^0xr Β-59 B-60 mra Β-61 B-62 Β-63 F B-64 H3C CH3 Β- 65 χυτίχχχ B-66 OL/?axr Β·67 B-68 ΧΜ^χα Β·69 —(CH2)n— η = 2~12 B-70 ch3 —(CH2)2-C-(CH2)2- ch3 Β·71 ch3 —(CH2)4-C-(CH2)3-ch3 B-72 CH3 CH3 -CH2-C-(CH2)2-C-(CH2)2-HH Β-73 03⁄4 CH3 -(^2 -0-(012)2-0-(012)3-HH B-74 CH3 -27- 201206996 [Table 4] Β·75 CH3 —(CH2)4-C-(CH2)5- Β-76 —( CH2)3-0-(CH2)2-0-(CH2)j- Β·77 ch3 ch3 —(CH2)3-Si-0—SHCH2)3-ch3 ch3 Β-78 η = 3~20 Β-79 n = 2~20 Β-80 mwxxcr η = 2~20 Β·81 n = 2 〜20 Β-82 ^κΓ2, ηΚ&gt;- η = 2~20 Β.83 XT ^-^〇-(CH2)nCH3 n = 5~19 Β-84 η = 5~19 Β-85 n = 〇~21 Β-86 η = 0 〜21 Β·87 η = 0 21 Β-88 γγ _ (^-CKCH2)nCH3 η = 0~21 Β*89 η = 0 〜21 Β-90 3-(Z)_0-(cH2)nCH3 η = 0~21 Β-91 η = 0 ~21 Β·92 /^°&quot;0\3^cH2&gt;nCH3 ΓΊ = 2~19 Β*93 η = 〇~21 Β·94 D_^^e^^_〇(CH2)nCH3 η = 0~21 Β-95 Β*96 -28- 201206996 [Table 5] B-97 ~0 0(CH2)nCH3 π = 〇~21 Β-98 jCrX^OUT (CH2)nCH3 η = 0~1彳Β·99 C5^ 〇(CH2)nCH3 π = 0-21 Β-100 O ο ο^〇(〇Η2)η〇Η3 η = 0~21 ΒΊΟΙ ο ° Β-102 ch3 H3cv^X3 Β-103 Β·104 ° Polyamide The tetracarboxylic dianhydride represented by the formula [3] used in the polymerization of the acid is not particularly limited, and may be one type of tetracarboxylic dianhydride or two or more kinds of tetracarboxylic dianhydride. As the tetracarboxylic dianhydride, tetracarboxylic dianhydride which is known as a raw material of polylysine can be used. Specific examples of the tetracarboxylic dianhydride include, for example, A of the formula [3] is a tetravalent organic tetracarboxylic acid dianhydride represented by A-1 to A-45 of the following Table 6. -29- 201206996 [Table 6] Α·1 Α·2 HsC ip ch3 Α·3 h3c ch3 Α·4 H3C ch3 —-----H3C ch3 Α-5 τγ Α-6 VC Α-7 Α-8 XX Α-9 xc A-10 :ΦΟ Α-11 )Κ Α-12 Fox A. 13 Α-14 Α·15 A* 16 Μ Α·17 Α-18 CH3 A_19 Α·20 Α·21 ch3 A-22 Α*23 x&gt;c Α-24 A-25 Α·26 )CC Α·27 »a A_28 Α·29 Α-30 -30- 201206996 [Table 7] Α-31 A-32 A-33 )DXC Α- 34 A-35 χΛχ A-36 Α·37 A-38 f3Q^cf3 OXC A-39 Α-40 ox A-41 ox A-42 Α_43 A-44 ch3 ybyc h3c A-45 Γ ?H3 i-OyC h3c The polymerization reaction of polylysine can be carried out by mixing a diamine component and a tetracarboxylic dianhydride component in an organic solvent. The organic solvent in this case is not particularly limited as long as it is a polylysine which is produced, and examples thereof include N,N-dimethylformamide and N,N-dimethylacetamidine. Amine, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl maple, trimethylamine hexamethyl phosphate, γ- Butyrolactone and the like. These can be used alone or in combination. Further, even a solvent in which polylysine cannot be dissolved can be used by being mixed in the solvent insofar as the produced polyamine does not precipitate. The water in the organic solvent hinders the polymerization of the poly-proline, and further causes the hydrolysis of the produced polyamine. Therefore, the organic solvent is preferably dried as much as possible. As a method of mixing the tetracarboxylic dianhydride component and the diamine component in an organic solvent, for example, a solution in which an organic solvent is dispersed or dissolved in a diamine component is stirred to form a tetracarboxylic dianhydride component. Adding or dissolving or dissolving the tetracarboxylic dianhydride component in an organic solvent as it is, and adding the diamine component to the organic solvent to disperse or dissolve the tetracarboxylic dianhydride. A method of adding a solution of a component, a method of adding a tetracarboxylic dianhydride component and a diamine component, and the like. Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of compounds, the components may be polymerized in a state in which they have been previously mixed, or may be sequentially polymerized individually. reaction. The temperature at which the polymerization of polyamic acid is generated is usually -2 0 to 150 ° C, preferably 0 to 100 t: and more preferably 10 to 80 ° C. The higher the temperature, the earlier the polymerization reaction will end. However, if it is too high, there will be a case where a high molecular weight polylysine cannot be obtained. Further, although the polymerization reaction can be carried out at any concentration, when the concentration is too low, it is 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 it is difficult to uniformly stir. It is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the polymerization reaction is carried out at a high concentration, and then an organic solvent may be added. The molecular weight of the obtained polyamic acid can be controlled by the molar ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization reaction. The closer the molar ratio is to 1:1, the larger the molecular weight will become. The molecular weight of the polyaminic acid used in the present invention or the polyimine obtained by dehydration of the polyamic acid, the ease of handling, and the stability of the properties at the time of forming the liquid crystal alignment film From the viewpoint of weight, the weight average molecular weight is preferably 2,000 to 200,000, more preferably 5,000 to 100,000 〇-32 to 201206996 &lt;polyimine&gt;&gt; Polyimine used in the liquid crystal alignment agent of the present invention The polyimine obtained by dehydration ring closure of polyamine. The dehydration ring closure reaction (amination reaction of polyimine from polyphthalamide) can be carried out by stirring the polyglycine in an organic solvent, a basic catalyst and an acid anhydride. As the basic catalyst, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctane. Among them, pyridine is further preferred because it has a moderate amount of the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and dianhydride. Among them, acetic anhydride is preferred because it is easy to purify the polyimine obtained by the ruthenium imidization. As a result, the ruthenium imidization ratio of the solution I polyimine used in the polymerization of the above polyamic acid can be controlled by adjusting the amount of the catalyst, the reaction, and the reaction time. The amount of the basic catalyst is 0.5 to 30 moles, more preferably 2 to 20 moles, per mole of the amine group. Further, it is preferably 1 to 50 moles, more preferably 3 to 3 parts, of the amidate group. The reaction temperature is preferably from -20 to 250 ° C, more preferably from 0 to 180 ° C. The imidization ratio of the polyimine used in the liquid crystal alignment agent must be 100%, or may be As the above-mentioned poly-proline or polyimine, it can be poured into a weak solvent with stirring, and precipitated and filtered. The weak solvent is not particularly limited, and examples thereof include methanol, propane, butyl cyanidin, heptane, methyl ethyl ketone, and methyl isobutyl group. Sex, therefore, after the coke honey bundle, the machine solvent I. The temperature should be good, the anhydride is 30 times Mo. This is not the recovery of ketone, ketone, B-33-201206996 alcohol, toluene, benzene, etc. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention can be obtained by dissolving at least one polymer selected from the group consisting of the above polyamidoximine in a medium. The liquid crystal alignment agent may be the same as the reaction solution of the above acid or polyimine, or may be diluted with the organic solvent. The organic solvent may be dissolved in the polymer or diluted in the reaction solution. The polymer can be dissolved, and the specific examples are not particularly limited, and examples thereof include N,N-dimethylformamide, methylethylamine, and N-methyl-2-pyrrolidone. N-methyl caprolide, N-ethylpyrrolidone, N-vinylpyrrolidine , diboron, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, ester, etc., which can be used in one kind or in a mixture of plural kinds. Further, even if it is alone, the polymer cannot be dissolved. The solvent is in a range in which the polymer component does not precipitate, and can be mixed into the alignment agent of the present invention. In particular, film uniformity can be applied to the substrate by being combined with a low surface tension. For example, ethyl acesulfame, butyl acesulfame, bisphenol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, propyl alcohol, 1- Ethoxy-2·propanol, 1-butoxy-2-propanol, keto-2-propanol, propylene glycol monoacetate, propylene glycol diacetate 'hub monomethyl ether-2-acetate, propylene glycol -1-monoethyl ether-2-acetic acid and polyorganosoluble polyamidamine should be used as a solution. Ν, Ν·2, 2-pyridyl γ- butyl, as long as the liquid crystal medium is mixed Ethyl card 1-methoxy-1-phenoxy 5 glycol-ester, di-34- 201206996 propylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, lactic acid The solid content concentration in the liquid crystal alignment agent of the present invention, such as a base ester, η-propyl lactate, η-butyl lactate, and isoamyl lactate, can be changed by the thickness of the liquid crystal alignment film formed. The point of forming a uniform and defect-free film is preferably 1 to 1% by mass, more preferably 2 to 8% by mass. Here, the solid content concentration in the liquid crystal alignment agent is contained. The content of the solid content in the liquid crystal alignment agent of the above polyamic acid and polyimine is in the present invention by placing the liquid crystal alignment agent in a baking box at 200 ° C for 2 hours. It is determined by dividing the weight of the liquid crystal alignment agent before being placed in the baking oven. The liquid crystal alignment agent of the present invention may contain, in the range which does not impair the effects of the present invention, the polyamic acid other than the above-mentioned polyamine and the polyaminic acid or the polyimine which uses the diamine of the present invention as a raw material. Yttrium. Further, it may contain a resin other than polyamine or polyimine. Further, in order to improve the adhesion of the coating film to the substrate, a conventional additive such as a decane coupling agent may be added. &lt;Liquid Crystal Alignment Film&gt; The liquid crystal alignment film of the present invention is a liquid crystal alignment film obtained by applying the liquid crystal alignment agent onto a substrate and calcining the liquid crystal alignment film. As a method of applying a liquid crystal alignment agent to a substrate, for example, a spin coating method, a printing method, an injection method, and the like, industrially, a transfer printing method such as fast-drying printing is widely used in terms of productivity. Even the liquid crystal alignment agent of the present invention can be suitably used in the order of -35 to 201206996. Further, the liquid crystal alignment agent is preferably used by filtering using a membrane filter having a pore diameter of 0.1 μm to Ιμπι. The drying step after applying the liquid crystal alignment agent is not essential, but from the viewpoint of obtaining a uniform coating film, it is preferred to include a drying step. This drying is not particularly limited as long as the solvent can be evaporated to such an extent that the shape of the coating film is not deformed. For the specific example, a method of drying at 50 to 150 ° C, preferably 80 to 120 ° C, for 0.5 to 30 minutes, preferably 1 to 5 minutes, may be employed. In the calcination after the application of the liquid crystal alignment agent, the condition is not particularly limited, and the solvent remaining in the coating film is extremely reduced, and from the viewpoint of not imparting damage to the coating film, it is preferably 150~ Calcination is carried out at 250 ° C, more preferably at 180 to 23 °C. This calcination can be carried out using a hot plate, a hot air circulating furnace, an infrared furnace or the like. The obtained liquid crystal alignment film has the ability to align the liquid crystal vertically. Further, by subjecting the liquid crystal alignment film to photo-alignment treatment, the liquid crystal can be aligned in a state of being vertically inclined only as a method of photo-alignment processing, and a conventional means can be applied. The wavelength of the light to be irradiated preferably contains light before and after 313 nm. The more the amount of light of this wavelength is irradiated, the larger the amount of tilt of the liquid crystal from vertical. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention is a liquid crystal alignment film obtained as described above. For example, after obtaining a substrate to which a liquid crystal alignment film of the liquid crystal alignment agent of the present invention is attached, a liquid crystal cell is prepared by a conventional method, and is made into a liquid crystal display element. The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is high in transparency, and a glass substrate or the like can be used. Further, when the substrate of the reflective liquid crystal display device is only a single substrate, an opaque material such as a germanium wafer may be used. In this case, a material such as aluminum or the like may be used. The thickness of the liquid crystal alignment film is not particularly limited, but is preferably from 5 n m to 300 nm, more preferably from 10 nm to 100 nm, from the viewpoint of the reliability of the liquid crystal display. When an example of a liquid crystal cell is used as an example, a pair of substrates on which a liquid crystal alignment film has been formed may be prepared, and a spacer may be spread on a liquid crystal alignment film of a single substrate so that the liquid crystal is aligned on the film surface to be inside. A method in which the other substrate is bonded, a 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 the substrate is bonded and sealed. The spacer thickness at this time is preferably Ιμηι 〜30μηη, more preferably 2μιη to ΙΟμπι. The invention is illustrated in more detail in the following examples, but the invention is not limited by the examples. [Embodiment] [Examples] The analysis apparatus and analysis conditions of 1H-NMR used in the examples are as follows. Apparatus: V aria η NMRS ystem 4 Ο Ο Ν Β (4 Ο Μ Μ Η ζ) Determination of solvent: CD C13, DMS Ο - d 6 -37- 201206996 Reference material: tetramethyl decane (TMS) (δΟ.Ο ppm For 'Η ) CDCI3 ( 577.0 ppm for l3C) <Example 1 &gt; (E ) -3,5-Diaminobenzyl-3-( 2-dodecyl-1,3-dioxirane oxime) Synthesis of porphyrin-5-yl) acrylate [Chem. 19]

A solution of 4 - propylene chloride (47.5 g, 524 mmol) in tetrahydrofuran (160 g) was added dropwise to 3,5-dinitrobenzyl alcohol (80.0 g, 404 mmol) and triethylamine at 〇 °C (55. lg, 545 mmol) in tetrahydrofuran (640 g) solution, then stirred for 1 hour. The reaction solution was poured into water to crystallize the product. The precipitated solid was separated by filtration and dried to give a crude product. The obtained crude product was washed with ethanol to obtain a dinitro compound (compound 1) as a yellow crystal (yield: 96.7 g, 96% yield). 'H-NMR ( CDC13 ) : δ 9.02 ( t, J = 2.2 Hz, 1 Η ) &gt; 8.58 ( m, 2 Η ) , 6.54 ( dd, J = 1 7.4 » 1.2 Hz &gt; 1 H ) » 6.24 (dd ' J = 1 7.4 &gt; 10·4Ηζ, 1 H ) , 5.99 ( dd, J = 1 0.4 &gt; 1.2 Hz , 1H ) , 5·39 ( s, 2H ). -38- 201206996 [Chem. 20]

ο 2 4-Bromophthalic anhydride (27.2 g, 120 mmol) and dodecylamine (24.4 g, 132 mmol) were dissolved in acetic acid (272 g), and refluxed at 120 ° C for 4 hours. The reaction liquid was poured into water to crystallize the product. The precipitated solid was separated by filtration and dried to obtain a crude product. The obtained crude product was washed with methanol to give 4-bromo-N-dodecylphthalimide (Compound 2) as white crystals (42.2 g, 88% yield)

• H-NMR (CDC13): δ 7.97 (m, 1H), 7.85 (m, 1H), 7.71 (m, 1H), 3.68 (t, J = 7.2 Hz, 2H), 1.66 ( m , 2H ) , 1.28 ( m &gt; 18H) , 0.8 7 ( t. J = 7 Ο Η z, 3H ) » [Chem. 21]

O

H-C12H2S Compound 2 (13.6 g, 60.0 mmol), Compound 1 ( 15.1 g, 60.0 mmol), triethylamine (7.28 g, 72.0 mmol), palladium acetate (0.134 g '0.600 mmol), and triphenyl The phosphine (0 · 3 1 4 g, 1.20 mmol) was dissolved in dimethylformamide (1 5 1 g) and stirred at 1 ° C for 6 hours. After completion of the reaction, the mixture was partitioned between chloroform and water, and the organic layer was dried over magnesium sulfate. The solvent of the organic layer obtained by filtration and removal of magnesium sulfate was evaporated, and then -39-201206996 was recrystallized from ethyl acetate to give a dinitro compound (compound 3) (18.6 g, 55% yield). 'H-NMR ( CDC13 ) : δ 9.04 ( t, J = 2.0 Hz, 1H), 8.62 ( d « J = 2.0 Hz, 2H ) , 8.03 ( s, 1H ) , 7.87 ( m &gt; 2H ), 7.85 ( d, J = 16.0 Hz, 1H), 6.69 (d, J = 1.6 Hz &gt; 1H), 5.46 (s, 2H), 3.69 (t - J = 7.4 Hz, 2H), 1.67 (m, 2H), 1.31 (m, 18H), 0.87 (t, J = 7.2 Hz). [化22]

Water (245 g) and ethyl acetate (279 g) were added to compound 3 (1 8.7 g '3 3.0 mmol), reduced iron (24.6 g, 396 mmol), and ammonium chloride (10.6 g, 198 mmol). Stir at 70 ° C for 4 hours. Filtration was carried out using hydrated stone at 70 ° C, ethyl acetate was separated from water, and the organic layer was dried over magnesium sulfate. After removing the magnesium sulfate by filtration, the organic layer was concentrated to give a crude material. After the obtained crude product was dissolved in tetrahydrofuran (18 7 g), activated carbon was added and stirred. After the activated carbon was removed by filtration, the organic layer was concentrated to give the desired diamine compound (Comp. 4) ( 15.5 g, 93% yield).

'H-NMR ( CDC13 ) : δ 7.98 ( s, 1H ) , 7.81 ( m, 3H )' 6.63 ( d, J = 1 6.4 Hz, 1 H ) , 6.1 6 ( d, J = 2.0 H z, 2 H ), 6.01 ( t, J = 2.0 Hz, 1 H ) , 5.09 ( s, 2H ) , 3.68 ( t - -40- 201206996 J = 7.6Hz &gt; 2H) ' 3.63 ( s ' 4H) » 1.67 ( m &gt ; 2 H ) * 1.28 (m, 18H) , 0 · 8 7 ( t ' J = 7.0Hz ' 3 H ). &lt;Example 2 &gt; Synthesis of (E)-3,5-diamino-based 3-(2-mercapto-1,3-di-isoxisoisoindol-5-yl)acrylate [ 23]

5 Using 4-bromophthalic anhydride (26.8 g, 118 mmol, decylamine (2 0.4 g '130 mmol) and acetic acid (268 g), the same reaction as the synthesis of the compound 2 was carried out to obtain a white solid. 4-bromo-N-fluorenyl phthalimide (Compound 5) (40.7 g, 94% yield). 'H-NMR (CDC13): δ 7.97 (d, J = 1 ·6 Ηζ,1 Η ) , 7.85 ( dd &gt; J = 7.8,1 ·6Ηζ,1Η), 7.70 ( d,J = 7.8Hz,1Η), 3.66 ( t,J = 7.2Hz,2H ) ,1.66 ( m · 2H ) &gt; 1.28 ( m , 14H ) , 0.87 ( t, J = 7.0 Hz ). [Chem. 24]

Compound 5 (36.3 g, 99.1 mmol), Compound 1 (25.lg '99.1 mmol), triethylamine (1 2.1 g, 1 1 9 mmol), palladium acetate-41 - 201206996 (0.223 g, 0.991 mmolO) were used. Triphenylphosphine (0.5 2 5 g, 1.9 8 mmol) and dimethylformamide (251 g) were reacted in the same manner as in the synthesis of compound 3 to obtain a dinitro compound (compound 6) ( 27.2 g ' 4 4% yield). ^-NMR ( CDC13 ) : δ 9·04 ( t, J = 2.4 Hz, 1H ) ' 8.63 ( d, J = 2.4 Hz, 2H ) ' 8.03 ( s - 1H ) , 7.86 ( m &gt; 3H ), 6.69 ( d, J = 16.0 Hz &gt; 1H ) , 5.46 ( s, 2H ) , 3.69 C t. J = 7.2 Hz - 2H ) , 1.67 ( m &gt; 2H ) , 1.42 ( m, 14H ), 0.87 ( t, J = 7.0Hz, 3H). [Chem. 25]

Compound 6 (20.0 g, 37.2 mmol), reduced iron (27.7 g '446 mmol), chlorinated saddle (1 1.9 g '2 2 3 mmol), water (120 g) and ethyl acetate (300 g) were used to carry out the compound. The synthesis of 4 was the same reaction to obtain the desired diamine compound (Compound 7) (1 6.7 g, 94% yield). 'H-NMR (CDC13) : δ 7.98 ( s &gt; 1 Η ) , 7.8 1 ( m, 3 Η ), 6.63 ( d, J = 16.4 Hz &gt; 1H ) , 6.16 ( d &gt; J = 2.0 Hz &gt 2H ) , 6.0 1 ( t, J = 2.0Hz, 1H ) , 5.09 ( s * 2H ) , 3.66 ( m, 6H ) , 1.67 ( m, 2H) , 1.28 ( m, 14H) , 0.87 ( t, J = 7.0Hz, 3H). -42-201206996 &lt;Example 3&gt; (E) -3,5-Diaminobenzyl-3-(2-octyl-1,3-diisooxisoindoline-5-yl)acrylate Synthesis [Chemistry 26] Ο

〇

NH2CeH17, AcOH using 4-bromophthalic anhydride (25.0 g, 110 mmol), octylamine (15.7 g, 121 mmol) and acetic acid (250 g), the same reaction as the synthesis of compound 2 was carried out as white Solid 4-bromo-N-octyl phthalimide (Compound 8) (36.0 g, 97% yield).

^-NMR (CDC13) : δ 7.97 ( dd, J = 1.6, 0.8 Hz, 1H ), 7.85 ( dd &gt; J = 7.8,1·6Ηζ, 1H ) , 7.7 1 ( dd, J = 7.8, 〇.8 Hz &gt; 1H ) , 3.66 ( t, J = 7.2 Hz, 2H ) , 1.66 ( m, 2H) , 1.28 ( m, 1 OH ) , 0.87 ( t. J = 7.0 Hz » 3H ). [化27]

Compound 8 (35.1 g, 103 mmol), Compound 1 (26.1 g, 103 mmol), triethylamine (12.6 g, 121 mmol), palladium acetate (0.232 g, 1.03 mmol), triphenylphosphine (0.542 g) And 2.06 mmol) and dimethylformamide (260 g) were subjected to the same reaction as the synthesis of Compound 3 to obtain a dinitro compound (Compound 9) (22.9 g, 44% -43 - 201206996 yield). ^-NMR ( CDC13 ) : δ 9.04 ( t, J = 2.0 Hz, 1H),

8.63 ( d ′ J = 2.0 Hz, 2H ) , 8.03 ( s, 1H ) , 7.86 ( m, 3H ), 6.69 ( d, J = 16.0 Hz ) , 5.09 ( s, 2H ) , 3.69 ( t,

J = 7.2 Hz, 2H), 1.67 (t, J = 7.2 Hz, 2H) 1.42 (m, 10H), 0-87 (t, J = 7.〇Hz, 3H). [化 28]

Compound 4 was carried out using compound 9 (20.Og, 39.3 mmol), reduced iron (29.2 g '47 1 mmol), ammonium chloride (12.6 g, 236 mmol), water (126 g) and ethyl acetate (300 g). The same reaction was carried out to obtain the desired diamine compound (Compound 10) (6.97 g, 34% yield). 'H-NMR (CDCI3) : δ 7.98 ( s,1Η ) , 7.81 ( m,3Η ), 6.63 ( d,J=16.0Hz « 1H ) , 6.16 ( d,J = 2.0Hz,2H ) ' 6.01 ( t , J = 2.0Hz, 1H ) , 5.09 ( s, 2H ) , 3.68 ( t, J = 7.2Hz « 2H ) , 3.63 ( s, 4H ) , 1.67 ( m, 2H ) , 1.28 (m, 1 OH ) , 0.87 ( t, J = 6_8Hz, 3H ). The compounds used in the following examples are abbreviated as follows. (tetracarboxylic dianhydride) 44- 201206996 PMDA : pyromellitic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride B0DA: bicyclo[3,3,0]octane-2 , 4,6,8-tetracarboxylic dianhydride (diamine) p-PDA: p-phenylenediamine PCH: 1,3-diamino-4-4-[4-(heptylcyclohexyl)phenoxy] Benzene DAI: (E) -3,5-diaminobenzyl-3-(2-dodecyl-1,3-di- oxo-iso-D-indoloxacin-5-yl)-propionic acid vinegar DA2 : ( E) · 3,5-Diaminobenzyl-3-(2-indolyl-1,3-di- oxaisoindoline-5-yl) acrylate DA3 : ( E ) -3,5- Aminobenzyl-3-(2-octyl-1,3-diisoxanthene-5-yl)acrylate [Chem. 29]

Ν~〇ι〇Η2ΐ

(Organic solvent) ΝΜΡ: Ν-methyl-2-pyrrolidone BC : butyl cyanidin &lt; molecular weight measurement&gt; The molecular weight of polyglycine or polyimine in the following examples was made by SSC Corporation. A room temperature gel permeation chromatography (GPC) apparatus (SSC-7200 - 45 - 201206996) and a column made by Shodex (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) 30mmol/L, tetrahydrofuran (THF) is l〇ml/L) Flow rate: 1.0ml/min. Quantitative line preparation standard sample: TSK standard polyethylene oxide made by Tosoh company (molecular weight about 9,000,000, 150,000, 1 00,000 &gt; 30,000 ), and Polyethylene glycol (molecular weight of approximately 1 2,000 ' 4,000 ' 1,000 ) manufactured by Polymer Laboratories. &lt;Example 4&gt; DA1 (0.60 7 g ' 1.20 mmol) and p-PDA (0.303 g, 2.80 mmol) were mixed in NMP (9.95 g), and stirred at room temperature for 1 hour to dissolve. PMDA (0.846 g, 3.88 mmol) was added, and the reaction was allowed to proceed at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (11.7 g) and BC (5.85 g) were added to the polyamic acid solution (11.7 G), and 6 mass% of the liquid crystal alignment agent (A) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 17,000 and a weight average molecular weight of 41,000. &lt;Example 5&gt; DAI (0.809 g, 1.60 mmol), and p-PDA (0.26G, -46-201206996 2.40 mmol) were mixed in NMP (10. 8 5 g), and stirred at room temperature for 1 hour to dissolve. After the addition of PMDA (0.846 G, 3.88 mmol), the reaction was allowed to proceed for 12 hours at room temperature to obtain a polyaminic acid solution. NMP (12.8 g) and BC (6.4 g) were added to the polyamic acid solution (12.8 g), and the mixture was stirred for 5 hours to obtain 6 mass% of the liquid crystal alignment agent (B). The polyamino acid had a number average molecular weight of 18,000 and a weight average molecular weight of 45,000 ° &lt;Example 6&gt; DA1 (0.7 5 9 g ' 1.50 mmol), and p-PDA (0.162 g, 1.50 mmol) were After mixing in NMP (8.78 g) and stirring at room temperature for 1 hour to dissolve, PMDA (0.628 g, 2 - 88 mmol) was added, and the reaction was allowed to stand at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (10. 3 2 g ) and 80: (5.168) were added to the polyamic acid solution (1.338), and 6 mass% of the liquid crystal alignment agent (C) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 12,000 and a weight average molecular weight of 31,000. &lt;Example 7&gt; DAI (1.0 g, 2.0 mmol) was mixed in NMP (8.13 g), and stirred at room temperature for 1 hour to dissolve. Then, PMDA (〇.423 g, 1.94 mmol) was added to the room. The reaction was allowed to proceed for 12 hours under temperature to obtain a polyaminic acid solution. NMP (9.56 g) and BC (4.7 8 g) were added to the polylysine solution (9 _ 5 6 g), and 6 mass% of liquid crystal was obtained by stirring for 5 hours. -47-201206996 aligning agent (D ). The polyamino acid had a number average molecular weight of 18 Å and a weight average molecular weight of 79,000 » &lt;Example 8&gt; DAI ( 2.275 g, 4.50 mmol) 'p-PDA (0.973 g, 9.0 mmol), and PCH (0.571 g, 1.50 mmol) was mixed in NMP (14. 6 g), and stirred at 40 ° C for 1 hour to dissolve. Then, BOD A (2.8 1 5 g ' 11.25 mmol ) and NMP (7.28 g) were added to 80 The reaction was allowed to proceed for 5 hours. Thereafter, CBDA (0.647 g, 3.30 mmol) and NMP (7.28 g) were added at 40 ° C for 10 hours to obtain a polyaminic acid solution. NMP was added to this polyamic acid solution (36.4 g) to be diluted to 6% by mass. Acetic anhydride (7-66 g, 75.0 mmol) and pyridine (2.37 g, 30.0 mmol) were added to the guanamine solution, and after stirring for 30 minutes, the reaction was allowed to proceed at 100 ° C for 3 hours. The precipitate obtained by dropping this solution in methanol (460 ml) was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to give a polyimine powder (E-1). The polyamidimide had an imidization ratio of 71%, a number average molecular weight of 13,000, and a weight average molecular weight of 42,000. NMP (74.0 g) was added to the obtained polyimine powder (E-1) ( In 6.0 g), the mixture was stirred at 50 ° C for 12 hours to dissolve. BCS (20.0 g) was added to the solution, and a liquid crystal alignment agent (E) was obtained by stirring at 50 ° C for 5 hours. -48-201206996 &lt;Example 9&gt; DA2 (0.716 g, 1.50 mmol), and p-PDA (0.162 g, 1.50 mmol) were mixed in NMP (8.58 g), and stirred at room temperature for 1 hour to dissolve Thereafter, PMDA (〇.635 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 (10 lg) and BC (5.04 g) were added to the polyamic acid solution (l?.g), and 6 mass% of the liquid crystal alignment agent (F) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 14,000 and a weight average molecular weight of 42,000. &lt;Example 10&gt; DA2 (〇.716g, 1.80 mmol) and p-PDA (0.108 g, 1.20 mmol) were mixed in NMP (7.67 g), and stirred at room temperature for 1 hour to dissolve, and then added. PMDA (0.529 g, 2.91 mmol) was allowed to react 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 the mixture was stirred for 5 hours to obtain 6 mass% of the liquid crystal alignment agent (G). The polyamine has a number average molecular weight of 16,000 and a weight average molecular weight of 68,000. &lt;Example 1 DA2 (0.836 g, 2.10 mmol), and p-PDA (0.081 g, 0.90 mmol) were mixed in NMP (8.1 9 g), and stirred at room temperature for 1 -49 to 201206996 hours to dissolve. PMDA (0.529 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 · 64 g ) and BC (4.82 g) were added to the polyamic acid solution (9.64 g), and a liquid crystal alignment agent (Η) of 6 mass% was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 15,000 and a weight average molecular weight of 59,000. &lt;Example 12&gt; DA3 (0.787 g, 2.10 mmol) and p-PDA (0.081 g, 0.90 mmol) were mixed in NMP (7.92 g), and stirred at room temperature for 1 hour to dissolve, and then added to PMDA. (0.529 g, 2.91 mmol) 'The reaction was allowed to proceed at room temperature for 12 hours' to obtain a polyaminic acid solution. NMP (9.3 lg) and BC (4.66 g) were added to the polyamic acid solution (9.31 g), and 6 mass% of the liquid crystal alignment agent (I) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 13,000 and a weight average molecular weight of 38,000. &lt;Example 13&gt; DA3 (0.899 g, 2.0 mmol) was mixed in NMP (7.52 g), and stirred at room temperature for 1 hour to dissolve, then added PMDA (0.428 g, 1.96 mmol) at room temperature The reaction was allowed to proceed for 12 hours to give a polyaminic acid solution. NMP ( 8.84 g) and BC (4.22 g) were added to the polyamic acid solution (8·8 4 g), and 6 mass% of the liquid crystal alignment agent (J)-50- was obtained by stirring for 5 hours. 201206996 The polyamino acid has a number average molecular weight of 12,000 and a weight average molecular weight of 42,000. &lt;Examples 14 to 23&gt; Using the liquid crystal alignment agents (A) to (?) obtained in Examples 4 to 13, a liquid crystal cell was produced by the procedure shown below, as shown below. The alignment of the liquid crystal and the measurement of the tilt angle were performed. [Production of Liquid Crystal Cell] The liquid crystal alignment agent (A) obtained in Example 4 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 ΙΟΟηηι. For this substrate, a linear polarized UV of 313 nm of an irradiation intensity of S.OmW/cnT2 was irradiated with 0 to 100 mJ. The direction of the incident light is inclined by 40° with respect to the normal direction of the substrate. The linearly polarized UV is obtained by passing the ultraviolet light of the high pressure mercury lamp through a 313 nm band pass filter through a 313 nm polarizing plate. Two sheets of the above substrate were prepared, and a glass bead spacer of 6 μm was spread on the liquid crystal alignment film of the other substrate, and then a sealing agent was printed thereon. 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 the antiparallel direction, and the sealing agent was thermally cured at 150 degrees for 105 minutes. 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 of -51 - 201206996. [Evaluation of Liquid Crystal Cell] For the liquid crystal cell, the presence or absence of an abnormal region when a voltage of 8 V was applied or removed at 25 °C was observed by a polarizing microscope, and the case where no abnormal region was observed 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 "AxoScan" manufactured by Axo Metrix Co., Ltd. by a Mueller matrix method. The ratio of each of the components of the tetracarboxylic acid dianhydride and the diamine used in the production of the liquid crystal alignment agents (A) to (J) is shown in Table 8 below. [Table 8] Example Liquid crystal alignment agent acid dianhydride (mol%) Diamine desert %) PMDA CBDA BODA DA1 DA2 DA3 d-PDA PCH 4 A 97 A _ 30 — _ 70 — 5 B 97 — _ 40 — _ 60 — 6 C 96 a _ 50 — a 50 — 7 D 97 — — 100 — — — — 8 E _ 22 75 30 — _ 60 10 9 F 97 _ — — 50 _ 50 — 10 G 97 — — _ 60 — 40 — 11 Η 97 一 — — 70 _ 30 — 12 I 97 — — — 70 30 — 13 τ 98 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — The results of the evaluation of the cells are shown in Table 9 below. -52- 201206996 [Table 9] Example Liquid crystal alignment agent uv irradiation amount Liquid crystal alignment pretilt angle No external voltage when applied voltage 14 A Om T Good defect 9 0° 5 0 0 m J Good good 8 9. 1° 1 0 0 0 m J Good good 8 8. 9° 15 B Om.I Good bad 9 0° 5 0 0 m T Good good 8 9. 7° 10 0 OmJ Good good 8 9. 6° 16 C Om T Good bad 9 0° 5 0 0 m T Good and good 8 9. 8° 10 0 OmJ Good and good 8 9. 8° 17 D Om T Good bad 9 0° 5 0 0 m T Good good 8 9. 9° 10 0 OmJ Good Good 8 9. 8° 18 E Om T Good bad 9 0° 5 0 0 m T Good good 8 9. 7° 10 0 OmJ Good good 8 9. 1° 19 F Om T Good bad 9 0° 5 0 Om T Good good 8 9. 5° 10 0 OmJ Good good 8 9. 1° 20 G Om T Good bad 9 0° 5 0 0 m T Good good 8 9. 8° 1 0 0 OmJ Good good 8 9. 7° 21 Η Om T Good bad 9 0° 5 0 0 m T Good good 8 9. 9° 10 0 OmJ Good good 8 9. 8° 22 I Om T Good bad 9 0° 5 0 Om T Good good 8 9. 4° 10 0 OmJ Good and good 8 9. 2° 23 J Om T Good or bad 9 0° 5 0 0 m T Good and good 8 9. 8° 10 0 OmJ Good and good 8 9. 7° From the above results, it was confirmed that the diamine compound of the present invention was used. The liquid crystal alignment film exhibits good vertical alignment energy. Further, by irradiating the polarized ultraviolet light to the liquid crystal alignment film of the present invention, it was confirmed that the liquid crystal was aligned in a state where the vertical direction was only inclined. From this, it is understood that the diamine compound of the present invention can be used as a liquid crystal alignment film for a liquid crystal display device of the vertical alignment type -53-201206996, and is also a useful compound for a liquid crystal alignment film used in a photo-alignment method. &lt;Example 2 4 &gt; DA-4: (E) -3,5-diaminobenzyl-3-(2-(4-butoxyphenyl)-I,3-dihydrooxonium Synthesis of porphyrin-5-yl) acrylate [4- 30] 4-Bromophthalic anhydride (34.76 g, 153 mmol), 4-butoxyaniline (23_00 g, 139 mmol) was added to acetic acid (184 g) The mixture was stirred under reflux for 2 hours. After the completion of the reaction, water (400 g) was added to the reaction liquid, and the precipitated crystals were filtered to obtain Compound 1 1 (4 9.9 6 g '134 mmol' 96% yield) [Chem. 31]

Compound 11 (26.20g, 7〇.〇mmol), Compound 1 (21.Olg^83.3 mmol), Tripotassium Phosphate (22.29g, 1 0.05 mmol), Palladium Chloride Acetonitrile Complex (〇.53g, 2.05) were used. Methyl), tris(o-tolyl)phosphine (1.25 g, 4.11 mmol), dimethylacetamide (160 g) 'The reaction was carried out at 1 1 ° C for 2 hours. Thereafter, the extraction was carried out by chloroform-water extraction, and the obtained organic layer was concentrated, and methanol was added to the obtained crude product to crystallize -54 - 201206996. The obtained crystal obtained by filtration was dissolved in toluene, and activated carbon (1 JOg) was added and stirred at 9 ° C for 1 hour. The solution was removed by hot filtration at 70 ° C to remove activated carbon ', and the obtained filtrate was concentrated, and the precipitated crystals were taken out by filtration and dried to give compound 12 (i7.35 g, 31.8 mmol, 45% yield) . [化32]

Compound 12 (17.35 g, 31.8 mmol), reduced iron (26.61 g, 477 mmol), ammonium chloride (5.35 g, 100 mmol) were added to a mixed solution of ethyl acetate (68 0 g) and water (48.15 g). The reaction was allowed to proceed at 75 ° C for 2 hours. Thereafter, the mixture was subjected to hot filtration at 75 ° C to remove the iron powder, and the obtained aqueous layer was removed using a separatory funnel, and activated carbon (1.0 1 g ) was added to the obtained organic layer. Stir at 75 ° C for 1 hour. After the reaction, the filtrate obtained by the hot filtration is subjected to an extraction operation with chloroform-water, and the obtained organic layer is dried by magnesium sulfate. The magnesium sulfate is removed by filtration, and the obtained organic layer is concentrated. The desired diamine compound 13 (13.098, 27. 〇111111 〇 1, 85% yield). δ'Η-NMR (CDC13) : δ 8 · 0 8 ( s, 1Η,), 7.95 (d,

1H, J = 8.0 Hz ) , 7.87 ( d, 1H, J = 8_0 Hz ) , 7.79 ( d, 1H &gt; J = 16.0 Hz) , 7.31 ( m, 2H) , 7.01 ( m - 2H ), 6.66 (d ,1H,J=16.0 Hz) &gt; 6.16 ( d &gt; 2H &gt; 3 = 2.0 Hz) ' 6.01 ( t,1H,J = 2.0 Hz ) , 5.09 ( s,2H ) , 4-00 ( t,2H • 55- 201206996 , J = 6.4 Hz) , 3.64 ( br-s, 4H ) , 1.79 ( m, 2H) » 1.50 (m, 2H ) , 0.99 ( t, 3H, J = 7.6 Hz). &lt;Example 25&gt; DA-5: (E) -3,5-Diaminobenzyl-3-(2-indolyl-1,3-di-isoxisoisoindol-4-yl)acrylate Synthesis [33]

A mixture of potassium permanganate (97.32 g, 616 mmol) and sodium hydroxide (5.09 g, 127 mmol) was dissolved in water (1500 ml), and 3-bromo-o-xylene 14 (22.67 g, 123 mmol) was added thereto. Heated under reflux for 4 hours. Thereafter, the produced manganese dioxide was removed by filtration, and after the filtrate was added to make the filtrate acidic to pH = 1, the solution was concentrated. Acetone (649 g) was added to the obtained concentrate, and the insoluble material was filtered over acetone, and the obtained filtrate was concentrated to give compound 15 (25.81 g, 105 mmol, 86% yield). [34]

Compound 15 (23. 83 g, 97.3 mmol) and mercaptoamine (18.2 6 g, 1 16 mmol) were added to acetic acid (13 Og), and stirred under reflux for 18 hours. Thereafter, 1 equivalent of hydrochloric acid (172 ml) was added to precipitate crystals. The crystals obtained by filtration through -56-201206996 were dried to give the compound 6 (3 3.2 2 g, 9 〇. 7 mmol, 93% yield). [化35]

Compound 16 (20.00 g, 54.6 mmol), Compound 1 (16.54 g, 65·6 mmol), diisopropylethylamine (M88 g, U5 mmol), palladium chloride acetonitrile complex (〇.42 g, 1.62) was used. Methyl), tris(p-tolyl)phosphine (〇.99g, 3·25 mmol), dimethylacetamide (165 ml) 'The reaction was carried out at 110 ° C for 2 hours. After that, the reaction mixture was concentrated, and the obtained crude product was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc 42% yield). [化36]

Compound 17 (1 1.58 g, 21.5 mmol), reduced iron (i8.05 g, 323 mmol), ammonium chloride (3.46 g, 64.7 mmol) was added to a mixed solution of ethyl acetate (80 g) and water (31.14 g). The reaction was carried out at 75 ° C for 2 hours. Thereafter, hot filtration was carried out as it was at 75 ° C. 'The iron powder was removed'. The aqueous layer was removed from the obtained filtrate using a separatory funnel' and activated carbon 201206996 (〇.60 g) was added to the obtained organic layer. Stir at 60 ° C for 1 hour. After the reaction, the filtrate obtained by the hot filtration was subjected to an extraction operation with ethyl acetate-water, and the obtained organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the obtained organic layer was concentrated, and the obtained powder was dissolved in ethyl acetate to purify the short column of the hydrazine gel to obtain the desired diamine compound 18 (7.258, 15.2 111111). 〇 1, 71% yield). ^-NMR (CDCI3) : δ 8.75 ( d,1H,J=16.0 Hz), 7.89 ( d,1H,J = 8.0 Hz) , 7.84 ( d &gt; 1H, J = 8.0 Hz), 7.69 ( t,1H , J = 7.6 Hz), 6.67 ( d &gt; 1H, J = 16.0 Hz), 6.20 ( d, 2H, J = 2.4 Hz), 6.00 ( t, 1H, J = 2.0 Hz), 5.11 ( s · 2H ) , 3.68 (t &gt; 2H, J = 7.2 Hz), 3.64 (br-s, 4H), 1.65 (m, 2H), 1.30 (m, 14H), 0.87 (t, 3H, J = 6.8 Hz). &lt;Example 26&gt; DA-6: (E)-3,5-Diaminobenzyl-3-(2-mercapto-6-methoxy-1,3-diiso-oxyisoindoline- Synthesis of 5-based) acrylates [Chem. 37]

Tetra-n-butylammonium tribromide (1 〇〇g, 2〇7 mmol) was dissolved in methylene chloride (1036 ml) and methanol (10 ml) to 3,4-dimethylanisole 19 (28.25 g, 207 mmol) was added to the solution and stirred at room temperature for 24 hours. Thereafter, potassium carbonate (41.50 g, 300 mmol) was added and stirred for 2012 hours, and the mixture was concentrated for 1 hour, and the obtained concentrate was subjected to extraction operation with toluene-water. The aqueous layer was removed, and the organic layer was dried over magnesium sulfate, and magnesium sulfate was removed by filtration. The obtained organic layer was concentrated to give Compound 20 (40.41 g, 188 mmol, 91% yield). [化381

Potassium peroxylate (135.llg, 855 mmol) and sodium hydroxide (6.8 Og, 170 mmol) were dissolved in water (2467 ml), and compound 20 (3 6.82 g, 171 mmol) was added thereto under reflux conditions. Heat for 3 hours. Thereafter, the produced manganese dioxide was removed by filtration, and the solution was concentrated by adding hydrochloric acid to make the filtrate acidic to pH = 1. Acetone (920 g) was added to the obtained concentrate, and the insoluble material was filtered in acetone, and the obtained filtrate was concentrated. 1 108 ml of ethyl acetate was added to the concentrate, and the insoluble matter was filtered in ethyl acetate. The obtained filtrate was concentrated to give Compound 2 1 (3 3.26 g '1 2 1 mmol, 7 1% yield). [化39]

Compound 21 (28.27 g, 103 mmol) and mercaptoamine (17.78 g, 1 1 3 mmo 1 ) were added to acetic acid (1 4 1 g), and stirred under reflux for 18 hours. Thereafter, 1 equivalent of hydrochloric acid (4000 ml) was added to precipitate crystals. The crystals obtained were recrystallized from hexane by filtration to give Compound 22 (19.55 g, 49.3 mmol, 49% yield). [40]

Compound 22 ( 15.71 g, 39.6 mmol), Compound 1 ( 12.01 g, 47.6 mmol), diisopropylethylamine (1〇9 g, 84·3 mmol), palladium chloride acetonitrile complex (〇.3 lg) 1,20 mm〇l), tris(p-tolyl)phosphine (〇_73g, 2.40 mmol), dimethylacetamide (120 ml) was reacted for 3 hours at U °C. Thereafter, the reaction liquid was concentrated, acetonitrile was added to the obtained crude product, and the precipitated solid was obtained by filtration. The obtained dark black powder was extracted with chloroform-water, the organic layer was separated, and the organic layer was concentrated, acetonitrile was added to the obtained crude product, and the precipitated solid was obtained by filtration to give compound 23 ( 6.97 g, 12.3 mmol, 31% yield). [化41]

Compound 23 (6.97 g, 12.3 mmol), reduced iron (10 g, 185 mmol), ammonium chloride (1_97 g, 36.8 mmol) was added to a mixed solution of ethyl acetate (78.6 g) and water (17.73 g). In the reaction, the reaction was carried out at 75 ° C for -60 - 201206996 for 4 hours. Thereafter, hot filtration was carried out as it was, and the iron layer was removed. From the obtained filtrate, the aqueous layer was removed using a separatory funnel, and activated carbon (〇.35 g) was added to the obtained organic layer. Stir at 60 ° C for 1 hour. After the reaction, the filtrate obtained by the hot filtration was subjected to an extraction operation with ethyl acetate-water, and the obtained organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the obtained organic layer was concentrated, and then purified to afford the desired diamine compound 24 (5.08 g, 1 〇. . ^-NMR (CDC13): δ 8.03 (d &gt; 1H, J = 16.0 Hz) ' 7.95 ( s, 1H) &gt; 7.36 ( s * 1H ) , 6.6 5 ( d, 1H, J = 16.0

Hz) , 6.16 ( d, 2H, J = 2.0 Hz) , 6.00 ( t, 1H &gt; J = 2.0 Hz) , 5.08 ( s, 2H) , 4.02 ( s, 3H) , 3.65 ( t, 2H, J = 7.2 Hz) , 3.63 ( m, 4H) &gt; 1.65 ( m &gt; 2H ) &gt; 1.30 ( m , 14H) &gt; 0.87 ( t &gt; 3H &gt; J = 6.8 Hz ). &lt;Example 27&gt; DA-4 (1.21 g, 2.5 mmol) was mixed in NMP (9.6 g), and stirred at room temperature for 1 hour to dissolve. Then, CBDA (0.48 g, 2.5 mmol) was added thereto. The reaction was allowed to proceed for 12 hours under temperature to obtain a polyaminic acid solution. NMP (5.7 g) and BC (11. 3 g) were added to the polyamic acid solution (1 1.3 g), and 6 mass% of the liquid crystal alignment agent (K) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 11,000 and a weight average molecular weight of 23,000. -61 - 201206996 &lt;Example 28&gt; DA-5 (1.02 g, 2.0 mmol) was mixed in NMP (7.93 g), and stirred at room temperature for 1 hour to dissolve, then added CBDA (0.38 g ^ 2.0 mmol) The reaction was allowed to proceed at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (4.7 g) and BC (9_3 g) were added to the polyamic acid solution (9.33 g), and 6 mass% of the liquid crystal alignment agent (L) was obtained by stirring for 5 hours. The polyamino acid had a number average molecular weight of 14,000' and a weight average molecular weight of 32,000. &lt;Example 2 9 &gt; DA-6 (0.96 g, 2.0 mmol) was mixed in NMP (7.60 g), and stirred at room temperature for 1 hour to dissolve, then CBDA (0.38 g ' 2.0 mmol) was added. The reaction was allowed to proceed at room temperature for 12 hours to obtain a polyaminic acid solution. NMP (4.5 g) and BC (8_9 g) were added to the polyamic acid solution (8.93 g), and 6 mass% of the liquid crystal alignment agent (M) was obtained by stirring for 5 hours. The polyamine has a number average molecular weight of 16,000 and a weight average molecular weight of 49,000. &lt;Examples 30 to 32&gt; Using the liquid crystal alignment agents (A) to (?) obtained in Examples 27 to 29, a liquid crystal cell was produced in the same manner as in the above Examples 14 to 23, as shown below. The alignment of the liquid crystal and the measurement of the tilt angle were performed. The ratio of each component of the tetracarboxylic dianhydride and the diamine used in the production of the above liquid crystal alignment agent (Κ) to (Μ) is shown in Table 10 - 62-201206996. Further, the evaluation results of the liquid crystal cell produced by using the above liquid crystal alignment agent (?) to (?) are shown in Table U below. [Table 10] Example Liquid crystal alignment agent acid dianhydride (mol%) Diamine (mol%) PMDA CBDA BODA DA-4 DA-5 DA-6 27 Κ — 98 — 100 — — 28 L — 98 — — 100 — 29 Μ — 98 — — — 100 [Table 11] Example Liquid crystal alignment agent UV irradiation amount Liquid crystal alignment pretilt angle No external voltage when applied voltage 30 Κ OmJ Good defect 90. 500mJ Good Good 89.8 lOOOmJ Good Good 89.7 31 L OmJ Good Bad 90. 500mJ Good Good 89.8 lOOOmJ Good Good 89.8 32 Μ OmJ Good Bad 90. 500mJ Good and good 89.9 lOOOOm Good and good 89.6 [Industrial use] The liquid crystal alignment agent of the present invention is used for a liquid crystal alignment film for a liquid crystal display element of a vertical alignment type, and is also used for a liquid crystal alignment film using a photoalignment method. in. Further, the diamine of the present invention is used in the production of a liquid crystal alignment agent, and is used as a raw material of polyglycolic acid or polyimine. The content disclosed in the specification of the present invention is the entire disclosure of the specification, the scope of the patent application, and the abstract of Japanese Patent Application No. 20 1 0-53 074, filed on July 5, 2010. Adopt the one. -63-

Claims (1)

201206996 VII. Patent application scope: 1. A liquid crystal alignment agent characterized in that it contains at least one selected from the group consisting of polylysine and polyimine obtained by dehydration of the polyamic acid. a polymer; wherein the polyamine is a diamine component represented by the following formula [2] containing a diamine represented by the following formula [1], and a tetracarboxylic acid represented by the following formula [3] The dianhydride component is obtained by polymerization; [Chemical 1] NH2 ° [1] (In the formula [1], S is a hydrogen atom, -CN, -〇(CH2)mCH3, -(CH2)mCH3 (m is an integer of 0 to 4), -NRl2- (R1, R2 are independent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a carboxyl group; p is a single bond, a phenyl group or a cyclohexyl group; Q is a single bond, or a bond group of -0-, -COO-; Is an alkyl group having a carbon number of 4 to 20), [Chemical 2] H2N-B-NH2 [2] (B in the formula [2] is a divalent organic group), -64-201206996 [Chemical 3] Ο Ο ο ο (The enthalpy in the formula [3] is a tetravalent organic group). 2. The liquid crystal alignment agent of the first aspect of the invention, wherein the diamine component represented by the above formula [2] contains 30 to 100 mol% of the diamine represented by the above formula [1]. 3. The liquid crystal alignment agent according to the first or second aspect of the invention, wherein the diamine represented by the above formula [1] is represented by the following formula [5], [Chemical 4] (In the formula [1], R is an alkyl group having a carbon number of 6 to 20). A liquid crystal alignment film obtained by coating and calcining a liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element having a liquid crystal alignment film according to item 4 of the patent application. 6. A kind of diamine, which is represented by the following formula [1], -65-201206996 [Chemical 5] (In the formula [1], S is a hydrogen atom, -CN, -0(CH2)mCH3 (m is an integer of 0 to 4), -NVR2- (R1, R2: or an alkyl group having 1 to 6 carbon atoms) , halogen atom 'or residue; base or cyclohexyl; Q is a single bond, or -0-, _C00-, the number of bonds 4 to 20). 7. The diamine of claim 6, wherein the diamine is represented by the following formula [5] '[6]'-(CH2)mCH3 turbidity is a hydrogen atom P is a single bond, a benzene junction Base; R is carbon, the above formula [1], h2n (wherein R is a hospital base with a carbon number of 6 to 20) ° 8. The diamine of the sixth paragraph of the patent application 'where' is the (E)-3,5-diaminobenzyl Base-3_(2·12$isoindoline-5-yl)acrylate, (E)-3,5-diamine 3 fluorenyl·1,3-dioxaisoindoline-5-yl Acrylate, diaminobenzyl-3 - (2-octyl-1,3-di- oxoisophthalic acid vinegar, (E)-3,5-diamino benzyl-3-(2) - (4 - D, the above formula [1] g -1,3 - di-side oxygen I benzyl-3-(2- or (E) -3,5--5-yl)propenyloxyphenyl)- -66 - 201206996 1,3-dioxaisoindoline-5-yl)acrylate, (benzyl-3-(2-indolyl-1,3-di-isoxisoisoporphyrin-4_ or ( E) -3,5-diaminobenzyl-3-(2-indolyl-6.methylisoindoline-5-yl) acrylate. 9. A poly-proline, which is included in the application The diamine component represented by the following formula [2] of the above-mentioned diamine is obtained by a polymerization reaction of a tetracarboxylic dianhydride component, [Chemical 7] H2N-B-NH2 [ 2 ] (in the formula [2] B is a divalent organic group), [Chemical 8] Q Ο E ) - 3,5 -diamino) acrylate, oxy-1,3 - II Lee oxygen item 6 ~ 8 range, with the following formula [3] 〇 Ο (A in the formula [3] is a tetravalent organic group).圔 圔 圔 醯 0 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 。 。 。 。 。 。 。 。 。 。 。 。 。 。 -67- 201206996 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201206996 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no