TW201544488A - Diamine synthesis and aligning agent of liquid crystal using the same - Google Patents

Abstract

The present invention discloses a polyimide resin for vertical aligning agent and its preparation, and provides a preparation method of side-chain diamine polyimide compound containing even and higher pre-tilting angle and able to be used as the raw material of polyimide aligning film and polyimide resin for vertical aligning agent by utilizing its 90 DEG pre-tilting angle and uniform and stable aligning property, and its preparation method.

Description

Diamine synthesis and liquid crystal alignment agent prepared therefrom

The invention relates to a polyimine resin for liquid crystal alignment agent and a preparation method thereof, in particular to a material which can be used as a raw material of a polyimide film with a good liquid crystal alignment property, which can easily control the pretilt angle. Method for preparing diamine compound, polyplylimic acid or polyimine coated with liquid crystal alignment agent prepared thereby, liquid crystal alignment agent containing same

In order to improve the performance of the display, various liquid crystal driving modes have been proposed and developed. The driving method of the liquid crystal display device is divided into a twisted nematic (TWist Nematic, hereinafter referred to as "TN") mode in which two types of transparent liquid crystal molecules are coated on the transparent electrode by an alignment film; Super Twist Nematic (hereinafter referred to as "STN") mode; plane conversion (hereinafter referred to as "IPS") mode; vertical alignment ("Vertical Alignment" (VA)) mode; using thin film transistor (Thin Film Transistor, under The TFT type called "TFT".

According to the above different driving modes, a specific pretilt angle is required, and the alignment film for stably generating such a pretilt angle becomes an important factor for determining the performance of the LCD.

As a material for the alignment film, a wide variety of materials ranging from inorganic substances to organic polymers have been used. A typical polymer compound which is most commonly used is a polymer such as a polyamidamide or a soluble polyimine which is used to convert a polyamine into an imine. Because of its good heat resistance and chemical resistance, it has been widely used in the industry as an alignment agent for alignment liquid crystals. On the other hand, such a polymer compound is obtained by polymerizing a diamine and a tetracarboxylic dianhydride, and the structure of the monomer realizes the material characteristics of the polymer compound.

The basic requirement for the alignment film is to control the pretilt angle. As is known, the shape of the alignment film surface and the length of the side chain significantly affect the pretilt angle of the liquid crystal molecules. The side chain structure is mainly introduced on the diamine or tetracarboxylic dianhydride, and in most cases, a diamine capable of easily linking the side chain is used. For example, Japanese Laid-Open Patent Publication No. Sho 64-25126, Japanese Laid-Open Patent Publication No. Hei No. 5--27244 discloses a polyamine or a polyamidiamine having a diamine such as a long-chain alkyl group as a raw material. Liquid crystal alignment agent.

Further, another polyimine liquid crystal alignment agent is widely known, and as the monomer, an aliphatic side chain type diamine in which a linear alkoxy group, an alkyl ester or a perfluoroalkyl group is used as a side chain is used. The side chain type polyimine has the characteristics of different alignment films depending on the aromatic or aliphatic component. The aromatic component is used as a hard core in a polymer chain, and its solubility in an organic solvent is low, so that industrial processability is unsatisfactory. Conversely, an aliphatic or cycloaliphatic alignment film can improve the above defects. However, the aliphatic polyamine-based alignment agent has a disadvantage that the liquid crystal alignment property is poor and the aliphatic soluble polyimide pigment has poor adhesion to the substrate, thereby slightly rubbing the coating film to be easily detached. In order to compensate for such shortcomings, there is also an alignment agent for mixing polyimine and poly-proline, but there is a problem of separation of the two due to heat, especially a liquid crystal alignment agent prepared by a block copolymerization method, and a preparation method thereof Too cumbersome question.

The previously proposed diamine having a side chain has a problem of controlling the efficiency according to the pretilt angle of the introduced amount or the efficiency of the polymerization reaction. If the reaction efficiency of the diamine is poor, the time required to polymerize the polymer compound is prolonged, and sometimes polymerization hardly occurs. If the polymerization time is elongated, industrial production problems are caused. If the polymerization of the polymer compound is insufficient, there is a problem in durability as a liquid crystal alignment film.

In view of the above problems, an object of the present invention is to provide a novel diamine compound which can increase the pretilt angle adjustment effect with a small amount of introduction amount, and which is excellent in polymerization efficiency, and a polyaminic acid or polyimine which is synthesized using the diamine, And a liquid crystal alignment agent comprising the polymer.

In order to achieve the above object, the present invention provides a diamine compound represented by the following Chemical Formula 1 which can be used as a raw material of a polyimide aligning film which can provide a good liquid crystal alignment property, and a method for producing the same. [Chemical Formula 1] (R _{1 in the} above Chemical Formula ₁ is When n=0, X ₁ is an alkyl end group having 12 to 20 carbon atoms, and when n=1, X ₁ is a CH ₂ linking group; n is 0 or 1; and X ₂ is selected from -O- or a linking group of -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -; Z ₁ and Z ₂ are each a single bond, or ; Y ₁ , Y ₂ , Y ₃ , Y ₄ are each H or F; Z _{3 is} selected from the group consisting of alkyl, fluoro, alkoxy, perfluoroalkyl, perfluoroalkoxy; a is between 0 and 5 Value).

According to the present invention, it is possible to prepare a diamine compound capable of easily controlling the pretilt angle of the liquid crystal, and to use the above diamine compound to maximize the interaction between the liquid crystal molecules and the side chain of the polyimide, and to have uniform and stable alignment. Liquid crystal alignment agent. Further, a liquid crystal alignment film obtained by using the above alignment agent and a liquid crystal display element including the liquid crystal alignment film are provided.

Some embodiments of the invention are described in detail below. However, the present invention may be widely practiced in other embodiments than the following description, and the scope of the present invention is not limited by the examples, which are subject to the scope of the following patents.

Unless otherwise defined, all technical and scientific terms used in the specification have the same meaning as commonly understood by those skilled in the art. The nomenclature used in this specification uses a manner that is conventional and common in the art.

The present invention discloses a diamine compound which can be used as a raw material of a polyimine aligning film which can easily control a pretilt angle and has good liquid crystal alignment property, a preparation method thereof, and a polyglycine for liquid crystal alignment agent prepared therefrom or Polyimine, and a preparation method thereof.

In order to achieve the above object, a process for producing a phenylenediamine derivative represented by the following Chemical Formula 1 is provided. [Chemical Formula 1] (R _{1 in the} above Chemical Formula ₁ is When n=0, X ₁ is an alkyl end group having 12 to 20 carbon atoms, and when n=1, X ₁ is a CH ₂ linking group; n is 0 or 1; and X ₂ is selected from -O- or a linking group of -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -; Z ₁ and Z ₂ are each a single bond, or ; Y ₁ , Y ₂ , Y ₃ , Y ₄ are each H or F; Z _{3 is} selected from the group consisting of alkyl, fluoro, alkoxy, perfluoroalkyl, perfluoroalkoxy; a is between 0 and 5 Value).

A method for producing a polyimine resin for a vertical alignment agent of a liquid crystal display device, comprising: (a) a side chain type diamine compound represented by the above Chemical Formula 1 and a chemical formula 2 represented by the following Chemical Formula 2 in a solvent a step of preparing a polyphthalic acid block copolymer by reacting a tetracarboxylic anhydride with a diamine compound having no side chain represented by Chemical Formula 3; and [Chemical Formula 2] The cycloaliphatic acid dianhydride represented by the above Chemical Formula 2 is selected from the group consisting of: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dihydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, trans-3,7-dibutylcyclooctane- 1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxytetrahydro-3 -furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornene-2:3,5:6-dianhydride , 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxy-3-furan) -naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5 -dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl- 5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5, 9b-hexahydro-7-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1 ,3,3a,4,5,9b-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan -1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5(tetrahydro-2,5-dioxo Benzyl-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl- 5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxytetrahydrofuran) 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxygen One or a combination of heterobicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), but is not limited thereto.

Further, the aromatic acid dianhydride represented by the above Chemical Formula 2 is selected from the group consisting of pyromellitic dianhydride, 4,4'-phthalic dianhydride, and 3,3',4,4'-benzophenone. Tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Anhydride, 3 3' 4 4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyldecane tetracarboxylic dianhydride, 3,3',4,4'-four Phenyl decane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic phenoxy)diphenyl sulfide dianhydride, 4, 4'-bis(3,4-dicarboxylic acid phenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxylic acid phenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyldiphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phosphine oxide dianhydride, P-Benzene-bis(triphenylphthalic acid) dianhydride, m-benzene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl Ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydrogen trimellitate), propylene glycol-double Trimellitic acid ester), 1,4-butanediol-bis(hydrogen trimellitate), 1,6-hexanediol-bis(hydroper trimellitate), 1,8-octanediol - one or a combination of bis(hydrogen trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitic acid ester), but is not limited thereto.

[Chemical Formula 3] The diamine represented by the above Chemical Formula 3 is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl hydrazine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzoquinone, 4 , 4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl )-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl Ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-amino) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 , 3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroindole, 2,7-diaminopurine, 9,9-bis(4-amino Phenyl) fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'- two Chloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(pair Phenylisopropyl ester) bisaniline, 4,4'-(m-isopropylidene) bisaniline, 2,2'-bis[4-(4-amino-2-trifluorophenoxy)benzene]hexafluoropropane , 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluoro Biphenyl, bis(4-aminophenyl)benzidine, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine, 1,1-m-xylylenediamine , 1,3-propanediamine, tetramethylenediamine, pentylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-diaminocyclohexane, isophor Ketodiamine, tetrahydrodicyclopentadienyldiamine, tricyclo[6.2.1.02,7]-undecene dimethyldiamine, 4,4'-subunit dicyclohexylamine, 1,3 An aliphatic or cycloaliphatic diamine such as bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyridine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyridine, 2,4-diamino-6-dimethylamino-1, 3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy -1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5- Triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-2-vinyl-s- Triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1, 2,4-triazole, 6,9-diamino-2-ethoxyacridine lactic acid, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopurine hydrate, 3,6 -diaminoacridine, bis(4-aminophenyl)aniline, 1-(3,5-diaminophenyl)-3-dodecylsuccinimide, 1-(3,5-diaminobenzene One or a combination of -3-octadecyl amber imines. (In the above Chemical Formula 2 and Chemical Formula 3, A is a tetravalent organic group constituting a tetracarboxylic acid; and R ₂ is a divalent organic group having no side chain.)

(b) a step of heat-treating the poly-proline-based block copolymer prepared by reacting the above Chemical Formula 2 and Chemical Formula 3, and converting it into a polyimine by a dehydration ring-closure reaction.

Further, the present invention provides a liquid crystal display element including the above liquid crystal alignment film.

The invention will be described in detail below.

The liquid crystal alignment material of the present invention is used to reduce steric hindrance due to side chains during polymerization, and two amino groups are substituted on each benzene ring as shown in the above Chemical Formula 1, and a methyl group is bonded to two benzene rings in which an amino group is substituted. In order to make the liquid crystals more uniformly aligned, the solubility and transparency to the organic solvent are remarkably improved. In this case, the side chain has an alkyl chain, an aromatic group, or a cycloaliphatic group as shown in the above Chemical Formula 1 in order to easily adjust the pretilt angle. According to this configuration, when the side chain has a ring-fat structure, the problem of a decrease in adhesion due to rubbing can be improved, and this effect is obtained.

These side chains in the above Chemical Formula 1 are designed to achieve the object of the present invention. The alkyl chain at the end of the side chain reduces the surface tension and forms a space in which the organic solvent penetrates between the polymer chains to increase the solubility.

And the aliphatic ring not only supports the liquid crystal molecules, but also connects the hard core with the terminal alkyl group into a strip shape like a liquid crystal, and when the liquid crystal is located around the side chain, the liquid crystal alignment property is improved by interaction with the liquid crystal side.

Further, a polyimine resin having a side chain determines the length of the diamine side chain and the length of the side chain interval depending on the average length of the long axis of the liquid crystal molecule and the desired pretilt angle. The present invention can adjust the properties of the polyimine copolymer by adjusting these factors.

The solvent in the step (a) of the above preparation method is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethyl hydrazine (DMSO), and Methylacetamide, γ-butyrolactone, hexamethylphosphonium triamine, hexamethylphosphoniumamine, tetrahydrothiophene hydrazine, tetramethylurea, p-chlorophenol, p-bromophenol, 2-chloro-4 One or more inactive solvents in the group consisting of hydroxytoluene, dioxane, tetrahydrofuran (THF), and cyclohexanone. The amount of the organic solvent to be used is usually adjusted to a total amount of the solid powder (diamine and dianhydride compound) of 0.1 to 30% by weight based on the total amount of the reaction solution.

The polyimine resin prepared by the above-described production method of the present invention is a polyimine resin for a liquid crystal alignment agent having a weight average molecular weight of 1,000 to 200,000.

Further, in the present invention, the side chain length of the above polyimine resin is 0.8 to 1.5 times the length of the long axis of the liquid crystal molecule, and the length between the side chains is 1.5 to 3.5 times the length of the long axis of the liquid crystal molecule.

Further, the present invention provides a liquid crystal alignment film produced by using a polyimine resin for a liquid crystal alignment agent of the above liquid crystal display device, and a liquid crystal display element comprising the same.

Next, a method for preparing a side chain type diamine polyimine resin for a liquid crystal alignment agent of the present invention will be described in detail.

The diamine compound of the above Chemical Formula 1 can be produced by the method of Reaction Formula 1 or Reaction Scheme 2.

First, when n = 1 in Chemical Formula 1, the preparation method of each step in Reaction Scheme 1 is as follows. [Reaction formula 1]

First step 4-(2,2-bis(4-aminophenyl)ethyl)benzene was added to the reaction vessel and dissolved in dichloromethane. After the dropwise addition of di-tert-butyl dicarbonate, the mixture was stirred, and water was added to the reaction vessel to complete the reaction, and then dichloromethane was extracted, and then all the organic solvents were evaporated. The obtained mixture was separated by column chromatography (cerium oxide, hexane/ethyl acetate = 1/1) to obtain a pale yellow solid di-tert-butyl (2-(4-hydroxyphenyl). Ethyl-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid.

Second Step The linking portion X ₂ is a linking group such as an ether group (-O-) or an ester group (-COO-), and these linking groups can be produced by a commonly used organic synthesis method.

Specifically, the corresponding halogen X ₃ substituted benzene derivative or halogen X ₃ substituted alkyl derivative in the ether and ester, and the hydroxyl derivative including the linking moiety X ₂ are subjected to basic conditions. reaction.

As a typical synthesis example, to prepare an ether group, di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl) bis(4,1-phenylene) is contained in a reaction vessel. The bis-carboxylic acid is dissolved in dimethylformamide (DMF), sodium hydroxide (NaOH) is added, the reaction is carried out at room temperature, and then the halogen-substituted compound to be attached is dissolved in dimethylformamide ( After DMF), the reaction was carried out to prepare. To prepare an ester group, di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid is placed in a reaction vessel. Dissolved in methyl chloride, adding carboxylic acid substituted compound, dicyclohexylcarbodiimide (DCC) (3.68 g, 17.86 mmol), 4-dimethylaminopyridine (DMAP) (0.22 g, 1.79 mmol) at room temperature Prepared by carrying out the reaction.

Third step After adding trifluoroacetic acid (TFA) to the tert-butoxycarbonyl protecting group in the previous step, the desired diamine compound is obtained by deprotecting the group.

Further, when n = 0 in Chemical Formula 1, the preparation method of each step of Reaction Scheme 2 is as follows. [Reaction formula 2]

First step After addition of bis(4-nitrophenyl)methane, the mixture was replaced with N ₂ , dissolved in toluene, and cooled to 0 ° C. After dissolving potassium ethoxide in 5 ml of ethanol (EtOH), it was slowly added dropwise to a solution having a temperature of 0 °C. After the temperature was raised to room temperature, the mixture was stirred for 4 hours, then filtered, and the filtered solid was washed with toluene, and then dried in a vacuum oven for 14 hours to obtain a blue-purple solid, bis(4-nitrophenyl)methane and potassium. salt.

The second step of constructing a single bond can be carried out in a variety of ways, for example, by a general organic synthesis method such as a Grinard reaction, a Friedel-Crafts deuteration method, or a Kishner reduction method. Connect properly.

Specifically, after dissolving bis(4-nitrophenyl)methane and potassium salts in dimethylformamide (DMF), the temperature was lowered to 0 °C. 1-bromohexadecane was slowly added dropwise. The temperature was raised to room temperature and stirred for 12 hours. (4,4'-heptadecane-1,1-diyl)bis(nitrobenzene) was obtained by column chromatography.

The third step for reducing the dinitro compound is not particularly limited, and as a catalyst, palladium carbon, platinum dioxide, Raney nickel, platinum black, ruthenium aluminum, platinum sulfide carbon, or the like is usually used, and ethyl acetate and toluene are used. The solvent such as tetrahydrofuran, dioxane or alcohol is subjected to hydrogen, hydrazine, hydrogen chloride or the like.

Specifically, after dissolving (4,4'-heptadecane-1,1-diyl)bis(nitrobenzene) in ethanol (EtOH), 5 wt% of Pd/C was slowly added. Add a large amount of hydrazine hydrate. After stirring at room temperature for 2 hours, the Pd/C was removed by filtration, and the solvent was distilled off under reduced pressure, and extracted with water (H ₂ O) and ethyl acetate (EA), and then obtained by column chromatography (4, 4) '-heptadecane-1,1-diyl) bis(diphenylamine).

Next, a polyimine resin prepared by using the diamine compound of Chemical Formula 1 and a process for producing the same are provided. The step of preparing a polyimine resin according to the chemical formula 1 according to the present invention, comprising: (a) a side chain type diamine compound represented by the above Chemical Formula 1 and a tetracarboxylic acid represented by Chemical Formula 2 in a solvent; a step of preparing an acid anhydride and a diamine compound having no side chain represented by Chemical Formula 3 to prepare a polyphthalic acid block copolymer of the following Chemical Formula 4; and [Chemical Formula 4] (b) a step of subjecting the above polyamic acid-based block copolymer to heat treatment to convert into a polyimine represented by Chemical Formula 5 by a dehydration ring-closure reaction. [Chemical Formula 5] (In the above Chemical Formula 4 and Chemical Formula 5, A is a tetravalent organic group constituting a tetracarboxylic acid; and B is a divalent organic group constituting a diamine derived from Chemical Formula 1 and Chemical Formula 3)

As a specific example, the side chain type diamine compound of the above Chemical Formula 1 and the diamine of the above Chemical Formula 3 are dissolved in a reaction solution of N-methyl-2-pyrrolidone, maintained at 5 ° C, and slowly added dropwise under a nitrogen atmosphere. After the tetracarboxylic dianhydride of the above Chemical Formula 2, it was stirred at room temperature for 6 hours to prepare a polyphthalic acid block copolymer. At this time, the viscosity can be adjusted by using a cellulose solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether.

Then, the present invention heat-treats the polyamine-based block copolymer at a temperature of 100 to 250 ° C for 30 minutes to 2 hours, and converts it into a polyimine by a dehydration ring-closure reaction.

Further, the polyglycolic acid may be stirred at 0 to 180 ° C for 1 to 100 hours under the conditions of a basic catalyst and an acid anhydride, and converted into a polyimine by a chemical diamine reaction. The obtained polyimine solution is preferably a precipitation separation method as mentioned in the synthesis of the above polyamic acid.

The solvent to be used in the preparation of the above polyamic acid is not particularly limited as long as it is capable of dissolving polyamic acid. As a specific example, there are N-methyl-2-pyrrolidone (NMP) and N,N-dimethyl group. Formamide (DMF), dimethyl hydrazine (DMSO), dimethyl acetamide, γ-butyrolactone, hexamethylphosphonium triamine, hexamethylphosphoniumamine, tetrahydrothiophene hydrazine, four Methyl urea, p-chlorophenol, p-bromophenol, 2-chloro-4-hydroxytoluene, dioxane, tetrahydrofuran (THF), cyclohexanone, and the like. Further, even if it is a solvent which cannot dissolve polylysine, it can be used in combination with the above solvent as long as it does not precipitate the produced polyamine. Further, since water in the organic solvent hinders the polymerization reaction and hydrolyzes the produced polyamic acid, it is preferred to use a dehydrated organic solvent.

In the tetracarboxylic anhydride in the polyproline preparation step, A is a tetravalent organic group. As a specific example, there are 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3', 4 , 4'-biphenyltetracarboxylic dianhydride (BPDA), 1,2,4,5- pyromellitic dianhydride (PMDA), cyclobutane tetracarboxylic dianhydride (CBDA) and 4-(2,5- Dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA) and the like.

Further, the diamine having a nitrogen atom in the above Chemical Formula 4 or Chemical Formula 5 is a divalent organic group constituting the above Chemical Formula 1. The benzyl derivative attached to the methylene group at the end of the diamine side chain may have liquid crystal alignment, and a large amount of the aromatic main chain and the side chain diamine, and the tetracarboxylic acid anhydride may increase the surface polarity while lowering the alignment film. The surface tension thus affects the adjustment of the pretilt angle. Also, the benzyl group attached to the diamine forms an organic solvent capable of penetrating into the space between the chains, thereby increasing solubility.

Further, in the diamine compound having a nitrogen atom in the above Chemical Formula 4 or Chemical Formula 5, a divalent organic group derived from Chemical Formula 3 (a diamine compound having no side substituent) can be used. Specifically, 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenebiscyclohexaneamine (PACM), 4,4'-methylene-2-methylcyclohexylamine (ANCAMINE) ), 4,4'-methylenediphenylamine, diaminobenzophenone, 4,4'-methylenediphenyldiamine (MDA), 4,4'-hexafluoroisopropyldiphenyl Diamine (6FDA), p-phenylenediamine (p-PDA), and the like.

In order to obtain a polyamic acid and react the tetracarboxylic dianhydride component and the diamine component in an organic solvent, it is usually preferably 5 ° C to 100 ° C. If the temperature is high, although the polymerization can be completed quickly, the molecular weight of the polymer becomes too high, so it is prudent. Further, when the reaction concentration is from 5% to 30% by weight, it can be uniformly stirred to obtain a desired molecular weight. The prepared polylysine may be used after being diluted with a reaction solution, or may be re-dissolved by precipitation separation. The poor solvent used in the precipitation separation is not particularly limited, and examples thereof include methanol, ethanol, hexane, acetone, butyl cellosolve, methyl ethyl ketone, toluene, benzene, diethyl ether and the like. The polyamic acid precipitate formed by adding a poor solvent is separated by filtration, washing, and then dried at room temperature under normal pressure or reduced pressure or dried by heating to obtain a solid powder.

In the above polyethylenimine side chain type, the divalent organic group R _{2 is} used for adding a liquid crystal alignment property, a solubility and a mold permeability to the polyimine, and the divalent organic group R _{2 having} no side chain is used. The distribution of side chain groups is determined by adjusting the spacing between the side chains. n in the above Chemical Formula 7 and Chemical Formula 8 is an integer of 1 to 10, more preferably 2 to 4.

The side chain length of the above-mentioned side chain type divalent organic group R ₂ is preferably 0.8 to 1.5 times the average length of the long axis of the liquid crystal molecule, and the length between the side chains is designed to be 1.5 times to 3.5 times the long axis length of the liquid crystal molecule. It is necessary to selectively determine the type and amount of the divalent organic group R ₂ having no side chain. By the above method, the polyimine has a good alignment property, and a polyimine resin having a specific structure having good properties in solubility, film permeability, and chemical stability can be prepared. The weight average molecular weight of the above polyimine resin is preferably from 1,000 to 200,000.

Furthermore, the present invention provides a liquid crystal alignment film using the polyimine resin, wherein the liquid crystal alignment film is coated on an patterned substrate by coating an alignment liquid comprising the polyamidene compound. The solvent to be used in the above-mentioned alignment liquid is not particularly limited as long as it is usually used for a liquid crystal alignment liquid and can dissolve the above polyimine compound, and contains 1 to 30% by weight of the above polyimine compound in the alignment liquid. It is better.

The liquid crystal alignment film of the invention has good liquid crystal alignment and rubbing resistance, and has high voltage holding ratio and high contrast, and the adjustment of the liquid crystal pretilt angle for reducing charge accumulation is relatively simple, and the side chain type diamine compound can be used. Maximize the interaction between the liquid crystal molecules and the side chain of the polyimide, and have a pretilt angle of 90 ° C, so that uniform and stable alignment can be obtained.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the scope of the invention is not limited to the above examples.

[Synthesis Example 1] Synthesis of di-tert-butyl (2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (di-tert-butyl ( (2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene))dicarbamate) After adding 4-(2,2-bis(4-aminophenyl)ethyl)benzene (15.0, 49.3 mmol) to a reaction vessel, dichloromethane (20 mL) was further added to dissolve. Di-tert-butyl dicarboxylate (24.9 mL, 108.4 mmol) was added dropwise to a reaction vessel in an ice bath and stirred at room temperature for 12 hours. After water was added to the reaction vessel to complete the reaction, dichloromethane was extracted, and then all the organic solvents were evaporated. The obtained mixture was separated by column chromatography (yield, hexane/ethyl acetate = 1/1) to yield a pale yellow solid (14.9 g, 61%). ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.20 (d, 4H), 7.06 (d, 4H), 6.81 (d, 2H), 6.61 (d, 2H), 6.35 (s, 2H), 4.50 (s , 1H), 1.53 (s, 18H).

Synthesis of 4-(2,2-bis(4-aminophenyl)methyl)benzene 4-(4,4,4-trifluorobutoxy)benzoic acid (4-(2,2-bis(4-aminophenyl)) Methyl)phenyl 4-(4,4,4-trifluorobutoxy)benzoate) Dissolving di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (9 g, 17.86 mmol) in a reaction vessel To methyl chloride (200 mL), 4-(4,4,4-trifluorobutoxy)benzoic acid (4.43, 17.86 mmol), dicyclohexylcarbodiimide (DCC) (3.68 g, 17.86 mmol), 4-Dimethylaminopyridine (DMAP) (0.22 g, 1.79 mmol) was reacted at room temperature for 12 hours to prepare 4-(2,2-bis(4-tert-butoxycarbonyl)methyl)benzene 4-(4, 4,4-Trifluorobutoxy)benzoic acid (9 g, 68%). Add 4-(2,2-bis(4-tert-butoxycarbonyl)methyl)benzene 4-(4,4,4-trifluorobutoxy)benzoic acid (7 g, 9.5 mmol) and three at 0 °C After fluoroacetic acid (TFA) (40 mL), the reaction was carried out for 1 hour to obtain 4-(2,2-bis(4-aminophenyl)methyl)benzene 4-(4,4,4-trifluorobutoxy)benzoic acid. (4g, 78%). ¹ H NMR (300 MHz, DMSO) δ 8.01 (d, 2H), 7.12 (m, 4H), 6.99 (d, 2H), 6.88 (d, 4H), 6.40 (d, 4H), 4.75 (s, 4H), 4.13 (t, 2H), 3.90 (t, 1H), 3.16 (d, 2H), 2.41 (m, 2H), 1.95 (m, 2H).

[Synthesis Example 2] Synthesis of 4-(2,2-bis(4-aminophenyl)ethyl)benzene 2,3',4',5'-tetrachloro-[1,1'-biphenyl]-4- 4-(2,2-bis(4-aminophenyl)ethyl)phenyl2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylate) Dissolving di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (9 g, 17.86 mmol) in a reaction vessel 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylic acid (4.83 g, 17.86 mmol), dicyclohexyl carbon two was added to dichloromethane (200 mL). Imine (DCC) (3.68 g, 17.86 mmol), 4-dimethylaminopyridine (DMAP) (0.22 g, 1.79 mmol), was reacted at room temperature for 12 hours to prepare 4-(2,2-bis(4-tert) Butoxycarbonyl)ethyl)benzene 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylic acid (9 g, 67%). Add 4-(2,2-bis((4-tert-butoxycarbonyl)amino)phenyl)ethyl)benzene 2,3',4',5'-tetrafluoro-[1,1' at 0 °C -Biphenyl]-4-carboxylic acid (9 g, 11.97 mmol) and trifluoroacetic acid (TFA) (50 mL), and reacted for 1 hour to obtain 4-(2,2-bis(4-aminophenyl)ethyl) Benzene 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylic acid (5 g, 74%). ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.19 (dd, 1H), 7.99 (d, 1H), 7.88 (d, 1H), 7.27-7.21 (m, 6H), 6.95 (d, 4H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9 (s, 4H, NH), 3.17 (d, 2H).

[Synthesis Example 3] Synthesis of 4,4'-(2-(4-(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl)diphenylamine (4,4' -(2-(4-(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl)dianiline) Dissolving di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5 g, 9.9 mmol) in a reaction vessel Methylformamide (DMF) (100 mL) was added with sodium hydroxide (NaOH) (1.6 g, 39.6 mmol) and reacted at room temperature for 1 hour to give 5-bromo-1,2,3-trifluorobenzene. (2.1 g, 9.9 mmol) was dissolved in dimethylformamide (DMF), and reacted for 5 hours to prepare di-tert-butyl(2-(4(3,4,5-trifluorophenoxy)phenyl) Ethyl-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5.5 g, 87%). Addition of di-tert-butyl(2-(4(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl) bis(4,1-phenylene) at 0 °C After dicarboxylic acid (5.5 g, 8.66 mmol) and trifluoroacetic acid (TFA) (30 mL), the reaction was carried out for 1 hour to obtain 4,4'-(2-(4-(3,4,5-trifluorobenzene). Oxy)phenyl)ethane-1,1-diyl)diphenylamine compound (3 g, 80%). ¹ H NMR (300 MHz, DMSO) δ 7.58 (t, 1H), 7.09 (d, 2H), 6.88 (m, 7H), 6.34 (d, 4H), 4.75 (s, 4H), 3.86 (t, 1H), 3.13 (d, 2H).

[Synthesis Example 4] Synthesis of 4,4'-(2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy) Phenyl)ethane-1,1-diyl)diphenylamine (4,4'-(2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl]] -4-yl)oxy)phenyl)ethane-1,1-diyl)dianiline) Dissolving di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5 g, 9.9 mmol) in a reaction vessel In dimethylformamide (DMF) (100 mL), sodium hydroxide (NaOH) (1.6 g, 39.6 mmol) was added and reacted at room temperature for 1 hour, 4-bromo-2,3',4', 5'-tetrafluoro-1-1'-biphenyl (3.02 g, 9.9 mmol) was dissolved in dimethylformamide (DMF), and reacted for 5 hours to prepare di-tert-butyl (2-(4(2) ,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethane-1,1-diyl) bis(4,1-Asia Phenyl) dicarboxylic acid (5 g, 73%). Addition of di-tert-butyl (2-(4(2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethyl at 0 °C After alkane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5 g, 7.23 mmol) and trifluoroacetic acid (TFA) (30 mL), react for 1 hour to obtain 4,4'- (2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethane-1,1-di Diphenylamine (3 g, 72%) compound. ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.00 (dd, 1H), 7.36-7.27 (m, 5H), 7.14 (d, 2H), 7.02-6.95 (m, 5H), 6.34 (d, 4H) , 4.44 (t, 1H), 3.9 (s, 4H, NH), 3.17 (d, 2H).

[Synthesis Example 5] Synthesis of 4,4'-(2-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl)diphenylamine (4, 4'-(2-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl)dianiline) Dissolving di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5 g, 9.9 mmol) in a reaction vessel In dimethylformamide (DMF) (100 mL), sodium hydroxide (NaOH) (1.6 g, 39.6 mmol) was added and reacted at room temperature for 1 hour, then 1-iodo-4-(4-pentyl) Benzyl)benzene (3.53 g, 9.9 mmol) was dissolved in dimethylformamide (DMF), and reacted for 5 hours to prepare di-tert-butyl (2-(4-(4-(4-pentylcyclohexyl))) Phenoxy)phenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (6 g, 81%). Addition of di-tert-butyl(2-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl) bis (4,1- sub) at 0 °C After phenyl)dicarboxylic acid (6 g, 8.02 mmol) and trifluoroacetic acid (TFA) (30 mL), the reaction was carried out for 1 hour to obtain 4,4'-(2-(4-(4-(4-pentylcyclohexyl)). Phenoxy)phenyl)ethane-1,1-diyl)diphenylamine (3 g, 77%). ¹ H NMR (300 MHz, CDCl ₃ ) δ7.33-7.35 (m, 6H), 7.14 (d, 2H), 6.95 (d, 4H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9 (s, 4H, NH), 3.17(d, 2H), 2.72 (m, 1H), 1.86-1.25 (m, 17H), 0.89 (t, 3H).

[Synthesis Example 6] Synthesis of 4,4'-(2-(4-(octyloxy)phenyl)ethane-1,1-diyl)diphenylamine (4,4'-(2-(4-( Octyloxy)phenyl)ethane-1,1-diyl)dianiline) Dissolving di-tert-butyl((2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5 g, 9.9 mmol) in a reaction vessel After adding sodium hydroxide (NaOH) (1.6 g, 39.6 mmol) to dimethylformamide (DMF) (100 mL) for 1 hour at room temperature, 1-bromooctane (1.91 g, 9.9 mmol) After dissolving with dimethylformamide (DMF), adding and reacting for 5 hours to prepare di-tert-butyl(2-(4-(octyloxy)phenyl)ethane-1,1-diyl) bis (4) , 1-phenylene)dicarboxylic acid (4 g, 66%). Add di-tert-butyl ((2-(4-(octyloxy)phenyl)ethane-1,1-diyl) at 0 °C After bis(4,1-phenylene)dicarboxylic acid (4 g, 6.53 mmol) and trifluoroacetic acid (TFA) (30 mL), the reaction was carried out for 1 hour to obtain 4,4'-(2-(4-(xin) Oxy)phenyl)ethane-1,1-diyl)diphenylamine (2g, 80%) compound. ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.18 (d, 2H), 6.95 (d, 4H ), 6.86 (d, 2H), 6.34 (d, 4H), 4.44 (t, 1H), 4.11 (t, 2H), 3.9(s, 4H, NH), 3.17(d, 2H), 1.74 (m, 2H), 1.43-1.26 (m, 10H), 0.89 (t, 3H).

[Synthesis Example 7] Synthesis of 4,4'-(heptadecane-1,1-diyl)dianiline In a reaction vessel, bis(4-nitrophenyl)methane (10 g, 38.7 mmol) was replaced with N ₂ and dissolved in toluene (100 ml). Potassium ethoxide (3.25 g, 38.7 mmol) was dissolved in ethanol (EtOH) (5 ml) and slowly added dropwise to a solution cooled to 0 °C. The temperature was raised to room temperature and stirred for 4 hours, and then filtered. The filtered solid was washed with toluene, and then dried in a vacuum oven for 14 hours to obtain a cyan purple solid bis(4-nitrophenyl)methane or potassium salt ( 10.35g, 90%). The bis(4-nitrophenyl)methane and potassium salt (10 g, 33.6 mmol) were dissolved in dimethylformamide (DMF) and then cooled to 0 °C. 1-Bromohexadecane (11.29 g, 36.99 mmol) was slowly added dropwise. The temperature was raised to room temperature and stirred for 12 hours. 4,4'-(heptadecane-1,1-diyl)bis(nitrophenyl) (11.37 g, 70%) was obtained by column chromatography. 4,4'-(heptadecane-1,1-diyl)bis(nitrophenyl) (10 g, 20.7 mmol) was dissolved in ethanol (EtOH) (100 ml), and Pd/C (5 wt. %). A large amount of hydrazine (41.44 g, 828 mmol) was added dropwise. After stirring at room temperature for 2 hours, it was filtered to remove Pd/C, and then the solvent was removed by distillation under reduced pressure. After extracting three times with water (H ₂ 0) and ethyl acetate (EA), 4, 4' was obtained by column chromatography. -(heptadecane-1,1-diyl)diphenylamine (7 g, 89%). ¹ H NMR (300 MHz, CDCl ₃ ) δ 6.95 (d, 4H), 6.34 (d, 4H), 3.96 (t, 1H), 3.9 (s, 4H), 1.89 (q, 2H), 1.33-1.25 (m, 14H), 0.8 (t, 3H).

[Example 1] 4,4'-methylenediphenylamine (2.97 g, 15.0 mmol) and diphenylamine (2.00 g, 3.7 mmol) obtained in the above Synthesis Example 1 were dissolved in N-methyl-2. a reaction solution of pyrrolidone (31.41 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.83 g, 9.4 mmol) and pyromellitic acid 2 over 2 hours. An anhydride (2.04 g, 9.4 mmol) was dissolved in a reaction solution of γ-butyrolactone (18.69 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 2] p-phenylenediamine (1.62 g, 15.0 mmol) and diphenylamine (2.00 g, 3.7 mmol) obtained in the above Synthesis Example 1 were dissolved in N-methyl-2-pyrrolidone (26.62 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.83 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (15.84 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 3] 4,4'-methylenediphenylamine (1.48 g, 7.5 mmol), p-phenylenediamine (0.81 g, 7.5 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 1 , 3.7 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (29.02 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (for 2 hours) 1.83 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.26 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Example 4] 4,4'-methylenediphenylamine (1.48 g, 7.5 mmol), p-phenylenediamine (0.81 g, 7.5 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 1 , 3.7 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (29.02 g), kept at room temperature, and 2,3,5-cyclotetracarboxylic dianhydride (2.10 g, 9.4) was slowly added dropwise over 2 hours. Methyl) and pyromellitic dianhydride (2.04 g, 9.4 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.82 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 5] 4,4'-methylenediphenylamine (2.85 g, 14.4 mmol) and diphenylamine (2.00 g, 3.6 mmol) obtained in the above Synthesis Example 2 were dissolved in N-methyl-2. a reaction solution of pyrrolidone (30.45 g), kept at room temperature, and slowly dropwise addition of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.76 g, 9.0 mmol) and pyromellitic acid 2 over 2 hours. An anhydride (1.96 g, 9.0 mmol) was dissolved in a reaction solution of γ-butyrolactone (18.12 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 6] p-phenylenediamine (1.55 g, 14.4 mmol) and diphenylamine (2.00 g, 3.6 mmol) obtained in the above Synthesis Example 2 were dissolved in N-methyl-2-pyrrolidone (25.85 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.76 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (15.38 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 7] 4,4'-Methylenediphenylamine (1.42 g, 7.2 mmol), p-phenylenediamine (0.78 g, 7.2 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 2 , 3.6 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (28.15 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (for 2 hours) 1.76 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were dissolved in a reaction solution of γ-butyrolactone (16.75 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Example 8] 4,4'-methylenediphenylamine (1.42 g, 7.2 mmol), p-phenylenediamine (0.78 g, 7.2 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 2 , 3.6 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (28.15 g), kept at room temperature, and 2,3,5-cyclotetracarboxylic dianhydride (2.01 g, 9.0) was slowly added dropwise over 2 hours. Methyl) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.28 g), and reacted for 6 hours to prepare a polyamidonic acid solution.

[Example 9] 4,4'-methylenediphenylamine (3.65 g, 18.4 mmol) and diphenylamine (2.00 g, 4.6 mmol) obtained in the above Synthesis Example 3 were dissolved in N-methyl-2. - a reaction solution of pyrrolidone (37.01 g), kept at room temperature, and slowly dropwise addition of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.26 g, 11.5 mmol) and pyromellitic acid 2 over 2 hours An anhydride (2.51 g, 11.5 mmol) was dissolved in a reaction solution of γ-butyrolactone (22.02 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 10] p-phenylenediamine (1.99 g, 18.4 mmol) and diphenylamine (2.00 g, 4.6 mmol) obtained in the above Synthesis Example 3 were dissolved in N-methyl-2-pyrrolidone (31.12 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.26 g, 11.5 mmol) and pyromellitic dianhydride (2.51 g, 11.5) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (18.51 g) and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 11] 4,4'-methylenediphenylamine (1.83 g, 9.2 mmol), p-phenylenediamine (1.00 g, 9.2 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 3 , 4.6 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (34.07 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (for 2 hours) 2.26 g, 11.5 mmol) and pyromellitic dianhydride (2.51 g, 11.5 mmol) were dissolved in a reaction solution of γ-butyrolactone (20.27 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 12] 4,4'-methylenediphenylamine (1.83 g, 9.2 mmol), p-phenylenediamine (1.00 g, 9.2 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 3 , 4.6 mmol) of the reaction solution dissolved in N-methyl-2-pyrrolidone (34.07 g), kept at room temperature, and slowly added 2,3,5-cyclotetracarboxylic dianhydride (2.58 g, 11.5) over 2 hours. Methyl) and pyromellitic dianhydride (2.51 g, 11.5 mmol) were dissolved in a reaction solution of γ-butyrolactone (20.95 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Example 13] 4,4'-methylenediphenylamine (3.00 g, 15.1 mmol) and diphenylamine (2.00 g, 3.8 mmol) obtained in the above Synthesis Example 4 were dissolved in N-methyl-2. a reaction solution of pyrrolidone (31.69 g), kept at room temperature, and slowly dropwise addition of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.86 g, 9.5 mmol) and pyromellitic acid 2 over 2 hours. An anhydride (2.06 g, 9.5 mmol) was dissolved in a reaction solution of γ-butyrolactone (18.85 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 14] p-phenylenediamine (1.64 g, 15.1 mmol) and diphenylamine (2.00 g, 3.8 mmol) obtained in the above Synthesis Example 4 were dissolved in N-methyl-2-pyrrolidone (26.84 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.86 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (15.97 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 15] 4,4'-methylenediphenylamine (1.50 g, 7.6 mmol), p-phenylenediamine (0.82 g, 7.6 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 4 , 3.8 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (29.27 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (for 2 hours) 1.86 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.41 g), and reacted for 6 hours to prepare a polyamidonic acid solution.

[Example 16] 4,4'-methylenediphenylamine (1.50 g, 7.6 mmol), p-phenylenediamine (0.82 g, 7.6 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 4 , 3.8 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (29.27 g), kept at room temperature, and 2,3,5-cyclotetracarboxylic dianhydride (2.12 g, 9.5) was slowly added dropwise over 2 hours. Methyl) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.97 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 17] 4,4'-methylenediphenylamine (2.98 g, 15.0 mmol) and diphenylamine (2.00 g, 3.8 mmol) obtained in the above Synthesis Example 5 were dissolved in N-methyl-2. - a reaction solution of pyrrolidone (31.50 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.84 g, 9.4 mmol) and pyromellitic acid 2 over 2 hours. An anhydride (2.05 g, 9.4 mmol) was dissolved in a reaction solution of γ-butyrolactone (18.74 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 18] p-phenylenediamine (1.62 g, 15.0 mmol) and diphenylamine (2.00 g, 3.8 mmol) obtained in the above Synthesis Example 5 were dissolved in N-methyl-2-pyrrolidone (26.69 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.84 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (15.88 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 19] 4,4'-Methylenediphenylamine (1.49 g, 7.5 mmol), p-phenylenediamine (0.81 g, 7.5 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 5 , 3.8 mmol) was dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.09 g), kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride was slowly added dropwise over 2 hours ( 1.84 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.31 g), and reacted for 6 hours to obtain a polyamidonic acid solution.

[Example 20] 4,4'-Methylenediphenylamine (1.49 g, 7.5 mmol), p-phenylenediamine (0.81 g, 7.5 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 5 , 3.8 mmol) The reaction solution dissolved in N-methyl-2-pyrrolidone (29.09 g) was kept at room temperature, and 2,3,5-cyclotetracarboxylic dianhydride (2.10 g, 9.4) was slowly added dropwise over 2 hours. Methyl) and pyromellitic dianhydride (2.05 g, 9.4 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.86 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Example 21] 4,4'-methylenediphenylamine (3.81 g, 19.2 mmol) and diphenylamine (2.00 g, 4.8 mmol) obtained in the above Synthesis Example 6 were dissolved in N-methyl-2. a reaction solution of pyrrolidone (38.30 g), kept at room temperature, and slowly dropwise addition of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.35 g, 12.0 mmol) and pyromellitic acid 2 over 2 hours. An anhydride (2.62 g, 12.0 mmol) was dissolved in a reaction solution of γ-butyrolactone (22.78 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 22] p-phenylenediamine (2.08 g, 19.2 mmol) and diphenylamine (2.00 g, 4.8 mmol) obtained in the above Synthesis Example 6 were dissolved in N-methyl-2-pyrrolidone (32.15 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.35 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (19.12 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 23] 4,4'-Methylenediphenylamine (1.90 g, 9.6 mmol), p-phenylenediamine (1.04 g, 9.6 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 6 , 4.8 mmol), a reaction solution dissolved in N-methyl-2-pyrrolidone (35.22 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (for 2 hours) 2.35 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were dissolved in a reaction solution of γ-butyrolactone (20.95 g), and reacted for 6 hours to obtain a polyamidonic acid solution.

[Example 24] 4,4'-Methylenediphenylamine (1.90 g, 9.6 mmol), p-phenylenediamine (1.04 g, 9.6 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 6 , 4.8 mmol) The reaction solution dissolved in N-methyl-2-pyrrolidone (35.22 g) was kept at room temperature, and 2,3,5-cyclotetracarboxylic dianhydride (2.69 g, 12.0) was slowly added dropwise over 2 hours. Methyl) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were dissolved in a reaction solution of γ-butyrolactone (21.67 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Example 25] 4,4'-methylenediphenylamine (3.75 g, 18.9 mmol) and diphenylamine (2.00 g, 4.7 mmol) obtained in the above Synthesis Example 7 were dissolved in N-methyl-2. a reaction solution of pyrrolidone (37.85 g), kept at room temperature, and slowly dropwise added 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.32 g, 11.8 mmol) and pyromellitic acid 2 over 2 hours. An anhydride (2.58 g, 11.8 mmol) was dissolved in a reaction solution of γ-butyrolactone (22.51 g), and reacted for 6 hours to prepare a polyamidonic acid solution.

[Example 26] p-phenylenediamine (2.05 g, 18.9 mmol) and diphenylamine (2.00 g, 4.7 mmol) obtained in the above Synthesis Example 7 were dissolved in N-methyl-2-pyrrolidone (31.79 g). The reaction solution was kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.32 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8) were slowly added dropwise over 2 hours. Methyl) was dissolved in a reaction solution of γ-butyrolactone (18.91 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Example 27] 4,4'-Methylenediphenylamine (1.88 g, 9.5 mmol), p-phenylenediamine (1.02 g, 9.5 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 7 , 4.7 mmol) was dissolved in a reaction solution of N-methyl-2-pyrrolidone (34.82 g), kept at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride was slowly added dropwise over 2 hours ( 2.32 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were dissolved in a reaction solution of γ-butyrolactone (20.71 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Example 28] 4,4'-Methylenediphenylamine (1.88 g, 9.5 mmol), p-phenylenediamine (1.02 g, 9.5 mmol) and diphenylamine (2.00 g) obtained in the above Synthesis Example 7 , 4.7 mmol) of a reaction solution dissolved in N-methyl-2-pyrrolidone (36.00 g), kept at room temperature, and slowly added 2,3,5-cyclotetracarboxylic dianhydride (2.65 g, 11.8) over 2 hours. Methyl) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were dissolved in a reaction solution of γ-butyrolactone (21.41 g), and reacted for 6 hours to obtain a polyaminic acid solution.

[Examples 29 to 56] The polyaminic acid solutions prepared in Examples 1 to 28 were dissolved in a solvent obtained by mixing γ-butyrolactone and butyl cellosolve to form a solution having a concentration of 5 wt% and using 0.1. The μm screening program was filtered to prepare a polyimine liquid crystal alignment agent.

[Comparative Example 1] 4,4'-methylenediphenylamine (1.52 g, 7.7 mmol), p-phenylenediamine (0.83 g, 7.7 mmol), and cholestyl-3-ol, 3,5-diamino Methyl benzoate (2.00 g, 3.8 mmol) was dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.51 g), kept at room temperature, and slowly added dropwise to 1,2,3,4-cyclobutane for 2 hours. Alkanetetracarboxylic dianhydride (1.88 g, 9.6 mmol) and pyromellitic dianhydride (2.09 g, 9.6 mmol) were dissolved in a reaction solution of γ-butyrolactone (17.56 g), and reacted for 6 hours to obtain a polyfluorene. Amino acid solution.

[Comparative Example 2] 4,4'-methylenediphenylamine (1.52 g, 7.7 mmol), p-phenylenediamine (0.83 g, 7.7 mmol), and cholestyl-3-ol, 3,5-diamino Methyl benzoate (2.00 g, 3.8 mmol) was dissolved in a reaction solution of N-methyl-2-pyrrolidone (30.46 g), kept at room temperature, and 2,3,5-cyclotetracarboxylic acid was slowly added dropwise over 2 hours. A dianhydride (2.14 g, 9.6 mmol) and pyromellitic dianhydride (2.09 g, 9.6 mmol) were dissolved in a reaction solution of γ-butyrolactone (18.12 g), and reacted for 6 hours to prepare a polyaminic acid solution.

[Comparative Examples 3 to 4] The polyphthalic acid solutions prepared in Comparative Examples 1 to 2 were prepared in the same manner as in the production methods of Examples 29 to 56 to prepare a liquid crystal alignment agent.

[Example 57] 1) Formation of Polyimine Alignment Film The liquid crystal alignment agents prepared in the above Examples 29 to 56 and Comparative Examples 3 to 4 were coated on a transparent conductive film by a spin coating method. On a glass substrate. After coating, it was calcined at 100 ° C for 30 minutes, and fired at 250 ° C for 1 hour to obtain a substrate having a polyimide film having a film thickness of 700 Å.

2) Preparation of liquid crystal display element The alignment film surface of the two substrates provided with the liquid crystal alignment film prepared as described above is not rubbed, but two substrates are arranged facing each other with a certain interval (liquid crystal layer gap), and two sheets are bonded with a sealant. At the edge portion of the substrate, liquid crystal is injected and filled into the cell gap formed by the substrate surface and the sealant, and the injection hole is closed to complete the liquid crystal panel. Further, the surface of the liquid crystal panel constitutes an opposing surface of each of the substrates of the liquid crystal panel, and the polarizing plate is bonded so that the polarization axis directions thereof are perpendicular to each other to obtain a liquid crystal display element. Here, as the sealant, a thermosetting resin is used, and as the separator, an epoxy resin containing alumina or the like is used. The characteristics of the pretilt angle, the two alignment property, and the like of the liquid crystal alignment agent obtained by applying the polyimide resin prepared in the present invention were evaluated by the following methods. The results are shown in Table 1 below. (1) The pretilt angle of the liquid crystal display element is carried out by spin crystallization according to the method described in the literature (TJ Schffer, et. al., J., Appl., Phys., vol. 19, 2013 (1980)). The measurement. 2 Alignment uniformity of liquid crystal The presence or absence of an abnormal quadrant in the liquid crystal panel when the voltage of the liquid crystal display element was turned on/off was observed with a microscope, and if there was no abnormal quadrant, it was judged as "good".

In the above examples, Examples 29 to 32 of the polyimine resin obtained by using the diamine of Synthesis Example 2 were applied to the twisted nematic (TN) mode (4 to 5°), and the diamine of Synthesis Example 4 was used. Examples 37 to 40 (1 to 2°) of the resulting polyimide resin are suitable for the planar conversion (IPS) mode.

Comparing the performance values of the comparative examples and the comparative examples, in addition to the examples 29 to 32 and 37 to 40 according to the present invention, other polylysines have more uniform alignment properties than the polylysines described in the comparative examples. A higher pretilt angle is required for the vertical alignment (VA) mode (89 to 90°).

The above-mentioned embodiments are merely illustrative of the technical idea and the features of the present invention, and the objects of the present invention can be understood by those skilled in the art and can be implemented according to the scope of the invention, that is, other Various equivalent changes or modifications may be made without departing from the spirit and scope of the invention, and are intended to be included within the scope of the invention.

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Claims (9)

A phenylenediamine derivative, wherein the phenylenediamine derivative is represented by the following Chemical Formula 1, [Chemical Formula 1] (R _{1 in the} above Chemical Formula ₁ is When n=0, X ₁ is an alkyl end group having 12 to 20 carbon atoms, and when n=1, X ₁ is a CH ₂ linking group; n is 0 or 1; and X ₂ is selected from -O- or a linking group of -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -; Z ₁ and Z ₂ are each a single bond, or ; Y ₁ , Y ₂ , Y ₃ , Y ₄ are each H or F; Z _{3 is} selected from the group consisting of alkyl, fluoro, alkoxy, perfluoroalkyl, perfluoroalkoxy; a is between 0 and 5 Value). A method for producing a polyimine resin for a vertical alignment agent for a liquid crystal display device, comprising: (a) a side chain type diamine compound represented by Chemical Formula 1 and a tetracarboxylic acid anhydride represented by the following Chemical Formula 2 in a solvent; And a step of preparing a polyamine group block copolymer by reacting a diamine compound having no side chain represented by Chemical Formula 3; and (b) subjecting the polyphthalic acid block copolymer of the step (a) to heat treatment, and dehydrating a step of converting a closed-loop reaction into a polyimine, [Chemical Formula 1] (The substituent in the above Chemical Formula 1 is the same as that described in Patent Application No. 1.) [Chemical Formula 2] [Chemical Formula 3] (In the above Chemical Formula 2 and Chemical Formula 3, A is a tetravalent organic group constituting a tetracarboxylic acid; and R ₂ is a divalent organic group having no side chain.) The method for producing a polyimine resin for a vertical alignment agent according to the liquid crystal display device of claim 2, wherein the diamine represented by the above Chemical Formula 3 is selected from the group consisting of: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl hydrazine, 3,3' -Dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzophenidine, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4 '-Aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminodi Benzene, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4 - bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4- Aminophenyl)-10-hydrogen hydrazine, 2,7-di Base, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4 '-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-di Aminobiphenyl, 1,4,4'-(p-isopropylisopropyl)diphenylamine, 4,4'-(m-isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino- 2-trifluorophenoxy)benzene]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2) -trifluoromethyl)phenoxy]-octafluorobiphenyl, bis(4-aminophenyl)benzidine, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole- 5-amine, 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-Diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, tricyclo[6.2.1.02,7]-undecene dimethyldiamine, 4 , an aliphatic or cycloaliphatic diamine such as 4'-subunit dicyclohexylamine or 1,3-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3 , 4-diaminopyridine, 2,4-diaminopyridine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4- Dihydroxypyridine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6 -Isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1 ,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2- Vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactic acid, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminohydrazine hydrate , 3,6-diaminoacridine, bis(4-aminophenyl)aniline, 1-(3,5-diaminophenyl)-3-dodecyl aminimide, 1-(3, One or a combination of 5-diaminophenyl)-3-octadecyl amber imine. The method for producing a polyimine resin for a vertical alignment agent of a liquid crystal display device according to claim 2, wherein the cycloaliphatic acid dianhydride represented by the above Chemical Formula 2 is selected from the group consisting of 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 3',4,4'-dicyclohexyltetracarboxylic dianhydride, trans-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2 ,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylate Anhydride, 3,5,6-tricarboxy-2-carboxynorbornene-2:3, 5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1, 3,3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan- 1,3-diketone, 1 ,3,3a,4,5,9b-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan -1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxo Benzyl-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 (four Hydrogen-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -8-ethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1 , 3-dione, 5-(2,5-dioxytetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5' Or one or a combination of the diketones; and the aromatic acid dianhydride represented by the above Chemical Formula 2 is selected from the group consisting of pyromellitic dianhydride, 4,4'-phthalic dianhydride, and 3,3' , 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 3 3' 4 4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyldecanetetracarboxylic dianhydride, 3 , 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic acid phenoxy Diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxylic acid phenoxy)diphenyl phthalic anhydride, 4,4'-bis(3,4-dicarboxylic acid benzene) Oxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyldicarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, double ( Phthalic acid) phosphine oxide dianhydride, p-benzene-bis(triphenylphthalic acid) dianhydride, m-benzene-bis(triphenylphthalic acid) dianhydride, bis(triphenyl-o-phenylene) Formic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydrogen trimellitate), Propylene glycol-bis(hydrogen trimellitate), 1,4-butanediol-bis(anhydrotrimellitate), 1,6-hexanediol-bis(anhydrotrimellitate), 1, 8- Xin Er One or a combination of alcohol-bis(hydrogen trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitic acid ester). The method for producing a polyimine resin for a liquid crystal alignment agent of a liquid crystal display device according to claim 2, wherein the solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N, N-II Methylformamide (DMF), dimethyl hydrazine (DMSO), hexamethylphosphoniumamine, cyclobutyl hydrazine, p-chlorophenol, p-bromophenol, 2-chloro-4-hydroxytoluene, dioxane, One or more inactive solvents in the group consisting of tetrahydrofuran (THF) and cyclohexanone. A liquid phase alignment agent for a liquid crystal display device is prepared by a polyamidene resin having a weight average molecular weight of 1,000 to 200,000 according to the production method described in claim 2 of the patent application. The polyimine resin according to claim 6, wherein the polyethylenimine resin has a side chain length of 0.8 to 1.5 times the length of the long axis of the liquid crystal molecule, and the length between the side chains is a long axis of the liquid crystal molecule. 1.5 to 3.5 times the length. A liquid crystal alignment film produced by using a liquid crystal alignment agent for a liquid crystal display device according to claim 6 of the invention. A liquid crystal display element comprising the liquid crystal alignment film according to item 8 of the patent application.