WO2015182925A1 - Novel diamine synthesis, and liquid crystal alignment agent using same - Google Patents

Abstract

The present invention relates to a polyimide resin for a vertical alignment agent and a method for preparing same and provides a method for preparing a side-chain diamine polyimide compound, which exhibits a uniform and high pretilt angle and thus can be used as a material for a polyimide alignment layer, and a polyimide resin for a vertical alignment agent, which has uniform and stable orientation and is capable of exhibiting a pretilt angle of 90° by using the method, and a method for producing same. To this end, the present invention provides a diaminobenzene derivative represented by chemical formula 1.

Description

New diamine synthesis and liquid crystal aligning agent using the same

The present invention relates to a polyimide resin for a liquid crystal aligning agent and a process for producing the same, and is a process for producing a diamine compound which can be used as a raw material for a polyimide alignment film which is easy to control the angle of pretilt angle and exhibits excellent liquid crystal aligning property and a polyamic acid Or a polyimide and a liquid crystal aligning agent containing the same.

Various liquid crystal driving modes have been proposed and developed to improve the display performance. The driving method of a liquid crystal display device is a twist nematic (TN) mode in which nematic liquid crystal molecules are arranged between two transparent electrode substrates coated with an alignment film on a transparent electrode, a super twist nematic twist nematic (hereinafter abbreviated as "STN") mode, an infinite switching (IPS) mode, a vertical alignment (VA) mode, and a thin film transistor Quot; TFT type ").

It is necessary to control a specific pretilt angle according to the driving mode, and an alignment film which stably generates the pretilt angle is an important factor for determining LCD performance.

Various materials have been applied to the alignment films from inorganic materials to organic polymer materials. Typical examples of the most frequently used polymer compounds include polymer compositions such as polyamic acid-based and soluble polyimide-based polymers that are imidized with polyamic acid. They are widely used industrially as an aligning agent for orienting a liquid crystal with excellent heat resistance and chemical resistance. On the other hand, these macromolecular compounds are formed by polymerization of diamine and tetracarboxylic acid anhydride, and the structure of the monomers causes the material properties of the polymer compound to be exhibited.

The basic requirement of the alignment film is control of the pretilt angle. It is known that the pretilt angle of the liquid crystal molecules is greatly influenced by the shape of the surface of the alignment film and the length of the side chains. In the side chain structure, a diamine or a tetracarboxylic acid is introduced into the anhydride. In most cases, a diamine which is easy to introduce a side chain group is used. For example, JP-A-64-25126 and JP-A-5-27244 have proposed a liquid crystal aligning agent comprising a polyamic acid or polyimide having a diamine having a long chain alkyl group as a raw material.

In addition, a polyimide liquid crystal aligning agent using an aliphatic side chain type diamine having a linear alkoxy group, an alkyl ester group, or a fluorinated alkyl group as a side chain is generally known. In the side chain-type polyimide, the characteristics of various alignment films differ depending on the aromatic system and the aliphatic system. Aromatic components act as hard cores in the polymer chain, resulting in low solubility in organic solvents and poor processability in industry. On the other hand, an alignment layer containing a large amount of an aliphatic or alicyclic group can improve the above disadvantages. However, the aliphatic polyamic acid-based alignment agent is inferior in orientation of the liquid crystal, and the aliphatic soluble polyimide has poor adhesiveness to the substrate, and peeling of the coating film tends to occur even in weak rubbing. In order to overcome such disadvantages, there is a problem that a polyimide and a polyamic acid are mixed with each other but they are separated by heat. Particularly, a liquid crystal aligning agent produced by a block copolymerization method of polyimide and polyamic acid has problems .

SUMMARY OF THE INVENTION

The diamine having side chains proposed in the prior art has a problem in that the efficiency of controlling the pretilt angle with respect to the amount of introduction and the reactivity at the time of polymerization are low. When the reactivity of the diamine is low, polymerization of the polymer compound takes time, and in some cases, polymerization hardly proceeds. If polymerization takes time, there is a problem in industrial production, and if the degree of polymerization of the polymer compound is insufficient, it becomes a problem from the viewpoint of durability as a liquid crystal alignment film.

The present invention relates to a novel diamine compound having a large effect of adjusting the angle of incidence and excellent in polymerization reactivity even with a small amount of introduction, and a polyamic acid or polyimide synthesized as a part of the diamine, and a liquid crystal alignment And the like.

In order to achieve the above object, the present invention provides a diamine compound represented by the following formula (1), which can be used as a starting material for a polyimide alignment film which is easy to control the angle of pretilt angle and exhibits excellent liquid crystal alignability, and a process for producing the same.

Formula 1

(R ₁ is in the formula (1)

X ₁ is an alkyl end group having 12 to 20 carbon atoms when n = 0, and X ₁ is a CH ₂ linking group when n = 1, and n is 0 or 1. X ₂ is -O- or -COO-, -OCO-, -CH ₂ O - a linking group selected _{from, Z -, - OCH 2 -} , -CF 2 O-, -OCF 2 -, -CH 2 CH 2 ₁ and Z < _{2 >} are independently a single bond,

or

Y ₁ , Y ₂ , Y ₃ and Y ₄ are independently H or F,

Z ₃ can be selected from alkyl, fluorine, alkoxy, fluoroalkyl, fluoroalkoxy, and a has a value between 0 and 5.)

DETAILED DESCRIPTION OF THE INVENTION AND SPECIFIC EMBODIMENTS

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

The present invention relates to a diamine compound which can be used as a raw material of a polyimide alignment film which is easy to control a pretilt angle and exhibits excellent liquid crystal alignment properties, a process for producing the same, a polyamic acid or polyimide for a liquid crystal aligner using the same, and a process for producing the same.

In order to achieve the above object, the present invention provides a diamine benzene derivative represented by the following formula (1) and a process for producing the same.

Formula 1

(R ₁ is in the formula (1)

ego,

X ₁ is an alkyl end group having 12 to 20 carbon atoms when n = 0, and X ₁ is a CH ₂ linking group when n = 1, and n is 0 or 1. X ₂ is -O- or -COO-, -OCO-, -CH ₂ O - a linking group selected _{from, -, - OCH 2 -,} -CF 2 O-, -OCF 2 -, -CH 2 CH 2

Z ₁ and Z ₂ are independently a single bond,

or

Y ₁ , Y ₂ , Y ₃ and Y ₄ are independently H or F,

Z ₃ can be selected from alkyl, fluorine, alkoxy, fluoroalkyl, fluoroalkoxy, and a has a value between 0 and 5.)

(a) reacting a side chain-type diamine compound represented by the formula (1) with a tetracarboxylic acid anhydride of the following formula (2) and a diamine compound having no side chain of the formula (3) in a solvent to prepare a polyamic acid-based block copolymer; And

(2)

Examples of the alicyclic acid dianhydrides of formula (2) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1 , 2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: Dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro- -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] -furan-l, 3,3a, 4,5,9b-hexahydro- -Dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro- 3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl Cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione) and the like.

Examples of the aromatic acid dianhydrides of Formula 2 include pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride , 3,3 ', 4,4'-biphenylether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3 ', 4,4'- 4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride Water, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ' , 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 ' Diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1 , 4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate) Bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), and the like, but are not limited thereto.

(3)

The diamine represented by the formula (3) is specifically exemplified by p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, Aminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'- Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) - trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'- diaminobenzophenone, 4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Bis (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenyl) hexafluoropropane, 2,2- 4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benz Benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenoxy) Aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'- -4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '- (p- Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoro-4,4'- 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octa, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, Aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 1,1-methoxysilylenediamine, 1, 3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamate 4,4'-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.02,7] undecylenedimethyldiamine, 4,4'-diaminocyclohexane, Aliphatic or alicyclic diamines such as 4'-methylenebis (cyclohexylamine) and 1,3-bis (aminomethyl) cyclohexane; Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- 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-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, Aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl) 3-jade Tetradecylsuccinimide, or combinations thereof.

Wherein A is a divalent organic group constituting a tetracarboxylic acid and R ₂ is a divalent organic group having no side chain group.

(b) heat-treating the polyamic acid-based block copolymer prepared by reacting the polyimide resin of the formula (2) and the polyimide resin of the formula (3) into a polyimide by a dehydration ring- to provide.

The present invention also provides a liquid crystal display element comprising the liquid crystal alignment layer.

Hereinafter, the present invention will be described in detail.

In order to reduce the steric hindrance caused by the side chain groups during polymerization, the liquid crystal alignment material of the present invention comprises two benzene rings each substituted with one amino group and one amino group substituted with a methyl group The liquid crystal is more uniformly oriented, and the solubility and transparency with respect to the organic solvent can be remarkably improved. At this time, the side chain is characterized by having an alkyl chain group, an aromatic group, and a fatty ring group as shown in Formula 1 so as to facilitate the adjustment of the angle of the preliminary crystal. These structures also have the effect of improving the adhesiveness due to rubbing when the side chain has a fatty ring system structure.

In the above formula (1), these side chains are designed to achieve the object of the present invention. The alkyl chain located at the end of the side chain lowers the surface tension and increases the solubility by making space for the organic solvent to penetrate between the polymer chains.

In addition, the aliphatic ring not only supports the liquid crystal molecule, but also the solid core group and the terminal alkyl group are connected in the form of a rod like a liquid crystal, and when the liquid crystal is placed around the side chain, the liquid crystal orientation can be increased by interaction with the side of the liquid crystal.

In the polyimide resin having a side chain, the length of the diamine side chain and the length of the side chain spacing are determined depending on the average length of the long axis of the liquid crystal molecule and the required size of the preliminary crystal. In the present invention, it is possible to control the characteristics of the polyimide-based copolymer by controlling these elements.

The solvent in step (a) may be at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethylacetamide, Chloro-4-hydroxytoluene, dioxane, tetrahydrofuran (THF), tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, ), And cyclohexanone, which is an inert solvent. The amount of the organic solvent is usually adjusted so that the total amount of the solid components (diamine and dianhydride compound) is 0.1 to 30% by weight based on the total amount of the reaction solution.

The polyimide resin produced by the production method of the present invention is a polyimide resin for a liquid crystal aligning agent of a liquid crystal display device having a weight average molecular weight of 1,000 to 200,000.

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

The present invention also provides a liquid crystal alignment film produced using the polyimide resin for a liquid crystal aligning agent of the liquid crystal display, and a liquid crystal display device including the same.

Hereinafter, a method for producing the side chain type diamine polyimide resin for a liquid crystal aligning agent of the present invention will be described in detail.

The diamine compound of Formula 1 may be prepared by a method similar to Reaction Scheme 1 or Reaction Scheme 2.

First, when n = 1 in the formula (1), the production method of each step of the reaction scheme 1 is as follows.

Scheme 1

Step 1

Add 4- (2,2-bis (4-aminophenyl) ethyl) phenol to the reaction vessel and dissolve in dichloromethane. After adding di-tert-butyl dicarbonate dropwise, the reaction mixture was stirred, and water was added to the reaction vessel to terminate the reaction. The reaction mixture was extracted with dichloromethane, and then all of the organic solvent was evaporated. The resulting mixture was purified by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain di-tert-butyl (2- (4-hydroxyphenyl) 1-phenylene)) dicarbamate.

Step 2

The connecting portion X ₂ is a bonding group such as an ether bond (-O-) or an ester bond (-COO-), and these bonding groups can be formed by a common organic synthesis method.

Specifically, this is a method of reacting a hydroxyl group derivative containing an ether, and the corresponding X ₃ is a halogen-substituted benzene derivative or a halogen-substituted alkyl derivative of X ₃ and X ₂ in the connecting ester under the presence of an alkali in general.

As an example of a typical synthesis, an ether bond is formed by dissolving di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1- phenylene) -dicarbamate in DMF, The reaction is carried out at room temperature, and the halogen-substituted compound to be connected is dissolved in DMF and reacted. (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene)) -dicarbamate was dissolved in Methylene Chloride, DCC (3.68 g, 17.86 mmol) and DMAP (0.22 g, 1.79 mmol) at room temperature.

Step 3

In the previous step, TFA was added to the t-BOC protecting compound and deprotecting to obtain the desired diamino compound.

When n = 0 in the formula (1), the production method of each step of the reaction formula (2) is as follows.

Scheme 2

Step 1

bis (4-nitrophenyl) methane, substitute with N ₂ , dissolve in toluene and reduce the temperature to 0 ° C. Potassium ethoxide is dissolved in 5 ml of EtOH and slowly added dropwise to a solution cooled to 0 ° C. The mixture was stirred at room temperature for 4 hours, filtered, washed with toluene, and then dried in a baking oven for 14 hours to obtain dark blue-violet solid bis (4-nitrophenyl) methane and potassium salt.

Step 2

There are various methods for single bonds, but they can be suitably connected using general organic synthesis methods such as Grinard reaction, Friedel-Crafts acylation method, Kishner reduction method, and the like.

Specifically, bis (4-nitrophenyl) methane and potassium salt are dissolved in DMF and the temperature is lowered to 0 ° C. Slowly add 1-bromohexadecane dropwise. The temperature is raised to room temperature and stirred for 12 hours. 4,4 '- (heptadecane-1,1-diyl) bis (nitrobenzene) is obtained by column chromatography.

Step 3

There is no particular limitation on the method for reducing the dinitro compound, and there is no particular limitation on the method for reducing the dinitro compound, and it is possible to use a catalyst such as palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium- Dioxane, or an alcohol-based solvent with hydrogen gas, hydrazine, hydrogen chloride, or the like.

Specifically, dissolve 4,4 '- (heptadecane-1,1-diyl) bis (nitrobenzene) in EtOH and slowly add 5 wt.% Pd / C. Hydrazine is added in excess. After stirring for 2 hours at room temperature, the mixture was filtered to remove Pd / C. The solvent was distilled off under reduced pressure, and extracted with H ₂ O and EA. 4,4 '- (heptadecane-1,1-diyl) dianiline .

Next, a polyimide resin prepared by using the diamine compound of the formula (1) and a process for producing the same are provided.

The step of preparing the polyimide resin from the formula (1) according to the present invention

(a) reacting a side chain-type diamine compound of the formula (1) with a tetracarboxylic acid anhydride of the formula (2) and a diamine compound not having a side chain group of the formula (3) in a solvent in the presence of a solvent to produce a polyamic acid- And

Formula 4

(b) heat-treating the polyamic acid-based block copolymer to convert it into a polyimide of the following formula (5) by a dehydration ring-closure reaction.

Formula 5

Wherein A is a tetravalent organic group constituting a tetracarboxylic acid and B is a divalent organic group constituting a diamine of the general formulas (1) and (3).

For example, the tetracarboxylic dianhydride of Formula 2 may be slowly reacted with the reaction solution of the side chain-type diamine compound of Formula 1 and the diamine of Formula 3 in N-methyl-2-pyrrolidone at 5 ° C, After the addition, the mixture is stirred at room temperature for 6 hours to prepare a polyamic acid-based block copolymer. At this time, the viscosity can be controlled by using a cellosolve solvent such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether and the like.

Thereafter, the polyamic acid block copolymer of the present invention can be thermally treated at 100 to 250 ° C for 30 minutes to 2 hours to convert it into a polyimide by a dehydration ring-closure reaction.

Also, polyamic acid can be converted to polyimide by chemical imidization reaction by stirring at 0 to 180 ° C for 1 to 100 hours in the presence of a basic catalyst and acid anhydride. The polyimide solution thus obtained is preferably precipitated and recovered as mentioned above in the synthesis of polyamic acid.

The solvent used for the production of the polyamic acid is not particularly limited as long as the polyamic acid is soluble, but specific examples thereof include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF) But are not limited to, sulfoxide (DMSO), dimethylacetamide, gamma -butyrolactone, hexamethylphosphoramide, hexamethylphosphoramide, tetramethylene sulfone, tetramethylurea, p-chlorophenol, -4-hydroxytoluene, dioxane, tetrahydrofuran (THF), cyclohexanone, and the like. Even if the solvent does not dissolve the polyamic acid, it may be mixed with the solvent in such a range that the produced polyamic acid is not precipitated. Furthermore, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the produced polyamic acid, it is preferable to use an organic solvent that is dehydrated and dried if possible.

A in the tetracarboxylic acid dianhydride in the production step of polyamic acid is a tetravalent organic group. Specific examples thereof include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3', 4,4'-biphenyltetracarboxylic acid (BPDA), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), cyclobutanetetracarboxylic dianhydride (CBDA) and 4- (2,5-ditoxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-carboxylic acid dianhydride (TDA).

The diamine having a nitrogen atom of the above formula (4) or (5) is a divalent organic group constituting the above formula (1). The benzyl group derivatives linked by the methylene group located at the terminal of the side chain of the diamine can exhibit liquid crystal aligning property. The main chain, the side chain diamine and the tetracarboxylic acid dianhydride containing a large amount of aromatic can increase the surface polarity and decrease the surface tension of the orientation film. It affects the control of the angle of incidence. In addition, the benzyl group to which the amine is linked may increase the solubility by creating a space through which the organic solvent can permeate through the chains.

The diamine compound having nitrogen atom in the above formula (4) or (5) may be a divalent organic group derived from the formula (3) (diamine compound having no side substituent). Specific examples thereof include 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenebiscyclohexylamine (PACM), 4,4'-methylene-2-methylcyclohexylamine (ANCAMINE) (MDA), 4.4'-hexafluoroisopropyldiphenyldiamine (6FDA), p-phenylenediamine (p-PDA) and the like .

When the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent to obtain the polyamic acid, the temperature is usually 5 to 100 ° C. Note that higher temperatures will terminate the polymerization sooner, but the molecular weight of the polymer can be too high. The reaction concentration is 5 to 30% by weight, and uniform stirring is carried out to obtain a required molecular weight. The obtained polyamic acid may be used by diluting the reaction solution and may be used by redissolution through precipitation. Examples of the poor solvent used for the precipitation recovery include, but are not limited to, methanol, ethanol, hexane, acetone, butyl cellosolve, methyl ethyl ketone, toluene, benzene and diethyl ether. The polyamic acid precipitate obtained by charging into a poor solvent may be recovered as a solid by filtration, washing and recovery, and then dried at room temperature or under reduced pressure or by heating and drying.

In the polyimide, the side chain type divalent organic group R ₂ is used for imparting the functionality of a polyimide such as liquid crystal aligning property, solubility and membrane permeability, and in the case of a _divalent organic group R ₂ having no side chain, Is used to determine the distribution of groups. In the formulas (7) and (8), n is an integer of 1 to 10, more preferably 2 to 4.

The side chain length of the branched-chain divalent organic group R ₂ is preferably adjusted so that the ratio of the average length of the long axis of the liquid crystal molecules is 0.8 to 1.5 times, and the length of the side chain groups is 1.5 to 3.5 times longer than the length of the long axis of the liquid crystal molecules. It is preferable to determine the type and amount of the _divalent organic group R 2 having no group. In this way, it is possible to produce a polyimide resin having a specific structure that exhibits excellent orientation properties in polyimide and excellent properties in terms of solubility, membrane permeability, and chemical stability. Preferably, the weight average molecular weight of the polyimide resin is 1,000 to 200,000.

Further, the present invention provides a liquid crystal alignment layer using the polyimide resin, wherein the liquid crystal alignment layer can be obtained by coating an alignment liquid containing the polyimide compound on a patterned substrate and then firing the liquid. The solvent used for the alignment solution is not particularly limited as long as it is usually used in a liquid crystal alignment solution and can dissolve the polyimide compound. Preferably, the alignment solution contains 1 to 30% by weight of the polyimide compound .

The liquid crystal alignment layer of the present invention is excellent in liquid crystal alignment and rubbing resistance, has a high voltage maintaining ratio and high contrast, can control the pretilt angle of a liquid crystal which can reduce charge accumulation, By maximizing the interaction effect between the side chains of the mid layer and having a 90 占 angle square, uniform and stable orientation can be obtained.

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

Synthesis Example 1

Synthesis of di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene)) dicarbamate

4- (2,2-bis (4-aminophenyl) ethyl) phenol (15.0 g, 49.3 mmol) was added to the reaction vessel and dichloromethane (200 mL) Di-tert-butyl dicarbonate (24.9 mL, 108.4 mmol) was added dropwise to the reaction vessel in an ice bath, followed by stirring at room temperature for 12 hours. Water was added to the reaction vessel to terminate the reaction, followed by extraction with dichloromethane, and all the organic solvent was evaporated. The resulting mixture was purified by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain a pale yellow solid (14.9 g, 61%).

^{1 H NMR (300 MHz, CDCl} 3) δ7.20 (d, 4H), 7.06 (d, 4H), 6.81 (d, 2H), 6.61 (d, 2H), 6.35 (s, 2H), 4.50 (s , ≪ / RTI > 1H), 1.53 (s, 18H).

Synthesis of 4- (2,2-bis (4-aminophenyl) ethyl) phenyl 4- (4,4,4-trifluorobutoxy) benzoate

To the reaction vessel were added di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene) -dicarbamate (9 g, 17.86 mmol) And DMAP (0.22 g, 1.79 mmol) was added to the reaction mixture, and the mixture was reacted at room temperature for 12 hours to obtain 4 (4,4,4-trifluorobutoxy) benzoic acid (4.43 g, 17.86 mmol) - (2,2-bis (4 - ((tert-butoxycarbonyl) amino) phenyl) ethyl) phenyl 4- (4,4,4-trifluorobutoxy) benzoate (9 g, 68%). 4- (4,4,4-trifluorobutoxy) benzoate (7 g, 9.5 mmol) was added to a solution of 4- (2,2-bis (4 - ((tert-butoxycarbonyl) amino) (4 g, 78%) of 4- (2,2-bis (4-aminophenyl) ethyl) phenyl 4- (4,4,4-trifluorobutoxy) benzoate was obtained by reacting the mixture at 0 ° C for 1 hour .

_{1 H NMR (300 MHz, DMSO} ) δ8.01 (d, 2H), 7.12 (m, 4H), 6.99 (d, 2H), 6.88 (d, 4H), 6.40 (d, 4H), 4.75 (s, 2H), 1.41 (m, 2H), 4.13 (t, 2H), 3.90 (t,

Synthesis Example 2

Synthesis of 4- (2,2-bis (4-aminophenyl) ethyl) phenyl 2,3 ', 4', 5'-tetrafluoro- [1,1'-biphenyl] -4-

The reaction vessel was charged with di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene) -dicarbamate (9 g, 17.86 mmol) in Methylene Chloride (3.83 g, 17.86 mmol), DCC (3.68 g, 17.86 mmol), DMAP (0.22 g, 1.79 mmol), 2,3 ', 4', 5'-tetrafluoro- [1,1'- biphenyl] -4- mmol) was added and reacted at room temperature for 12 hours to obtain 4- (2,2-bis (4 - ((tert-butoxycarbonyl) amino) phenyl) ethyl) phenyl 2,3 ', 4', 5'-tetrafluoro- [ , 1'-biphenyl] -4-carboxylate (9 g, 67%).

Phenyl) ethyl] phenyl 2,3 ', 4', 5'-tetrafluoro- [1,1'-biphenyl] -4-carboxylate (prepared by reacting 4- (2,2- (4-aminophenyl) ethyl) phenyl 2,3 ', 4', 5'-tetramethyluronium tetrafluoroborate was prepared by adding TFA (50 ml) at 0 ° C and reacting for 1 hour. tetrafluoro- [1,1'-biphenyl] -4-carboxylate (5 g, 74%).

^{1 H NMR (300 MHz, CDCl} 3) δ8.19 (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, IH), 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) dianiline

To the reaction vessel was added di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) After dissolving, 5-bromo-1,2,3-trifluorobenzene (2.1 g, 9.9 mmol) was dissolved in DMF and reacted for 5 hours. Preparation of di-tert-butyl ((2- (4- (3,4,5-trifluorophenoxy) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) dicarbamate Respectively. bis (4,1-phenylene)) dicarbamate (5.5 g, 8.66 mmol) was reacted with di-tert-butyl (2- (4- (3,4,5-trifluorophenoxy) phenyl) ethane- TFA (30 mL) was added at 0 ° C and the reaction was carried out for 1 hour to give 4,4 '- (2- (4- (3,4,5-trifluorophenoxy) phenyl) ethane-1,1-diyl) dianiline compound 3 g, 80%).

^{1 H NMR (300 MHz, DMSO} ) δ7.58 (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

4,4 '- (2- (4 - ((2,3', 4 ', 5'-tetrafluoro- [1,1'-biphenyl] -4-yl) oxy) phenyl) ) dianiline synthesis

To the reaction vessel was added di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene) -dicarbamate (5 g, 9.9 mmol) 4-bromo-2,3 ', 4', 5'-tetrafluoro-1-1'-biphenyl (3.02 g, 9.9 mmol) was added to the reaction mixture at room temperature for 1 hour. DMF and reacted for 5 hours to obtain di-tert-butyl ((2- (4 - ((2,3 ', 4', 5'-tetrafluoro- [1,1'- biphenyl] 1,1-diyl) bis (4,1-phenylene)) dicarbamate (5 g, 73%). di-tert-butyl ((2- (4 - ((2,3 ', 4', 5'-tetrafluoro- [1,1'- biphenyl] -4-yl) oxy) (4 - ((4 - ((2, 1, 2, 3,3-dioxolane) , 3 ', 4', 5'-tetrafluoro- [1,1'-biphenyl] -4-yl) oxy) phenyl) ethane-1,1-diyl) dianiline (3 g, 72%).

^{1 H NMR (300 MHz, CDCl} 3) δ8.00 (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, IH), 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) dianiline

To the reaction vessel was added di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene) -dicarbamate (5 g, 9.9 mmol) NaOH (1.6 g, 39.6 mmol) was added to the reaction mixture and the mixture was reacted at room temperature for 1 hour. Then, 1-iodo-4- (4-pentylcyclohexyl) benzene (3.53 g, 9.9 mmol) 1,1-diyl) bis (4,1-phenylene)) dicarbamate (6 g, 81%) was prepared in the same manner as in . 1,1-diyl) bis (4,1-phenylene)) dicarbamate (6g, 8.02mmol) was added to a mixture of di-tert- butyl ((2- (4- TFA (30 ml) was added at 0 ° C and the reaction was carried out for 1 hour to give 3 g of 4,4 '- (2- (4- (4- (4-pentylcyclohexyl) phenoxy) phenyl) ethane-1,1-diyl) dianiline , 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

4,4 '- (2- (4- (octyloxy) phenyl) ethane-1,1-diyl) dianiline Synthesis

To the reaction vessel was added di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene) -dicarbamate (5 g, 9.9 mmol) (1.91 g, 9.9 mmol) was dissolved in DMF and reacted for 5 hours to obtain di-tert-butyl ((2- ( Bis (4,1-phenylene)) dicarbamate (4 g, 66%) was prepared. (4 g, 6.53 mmol) was added to TFA (30 ml) at 0 ° C, and the mixture was stirred at -78 ° C for 1 h. Dianiline (2 g, 80%) was obtained in the same manner as in Example 1, and the reaction was carried out for 1 hour to obtain a 4,4 '- (2- (4- (octyloxy) phenyl) ethane-1,1-

^{1 H NMR (300 MHz, CDCl} 3) δ7.18 (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

Add bis (4-nitrophenyl) methane (10 g, 38.7 mmol) to the reaction vessel, replace with N ₂ , dissolve in toluene (100 ml) and reduce the temperature to 0 ° C. Potassium ethoxide (3.25 g, 38.7 mmol) is dissolved in 5 ml of EtOH and slowly added dropwise to a solution cooled to 0 ° C. The mixture was stirred at room temperature for 4 hours, filtered, washed with toluene, and then dried in a baking oven for 14 hours to obtain a dark purple solid bis (4-nitrophenyl) methane, potassium salt (10.35 g, 90% . After dissolving bis (4-nitrophenyl) methane, potassium salt (10 g, 33.6 mmol) in DMF, the temperature is lowered to 0 ° C. 1-bromohexadecane (11.29 g, 36.99 mmol) is slowly added dropwise. The temperature is raised to room temperature and stirred for 12 hours. 4,4 '- (heptadecane-1,1-diyl) bis (nitrobenzene) (11.37 g, 70%) was obtained by column chromatography. After dissolving 4,4 '- (heptadecane-1,1-diyl) bis (nitrobenzene) (10 g, 20.7 mmol) in 100 ml of EtOH, slowly add 5% Pd / C. Hydrazine (41.44 g, 828 mmol) is added dropwise. After stirring at room temperature for 2 hours, the mixture was filtered to remove Pd / C. The solvent was distilled off under reduced pressure and the mixture was extracted three times with H ₂ O and EA. 4,4 '- (heptadecane-1,1-diyl) dianiline 7 g, 89%).

^{1 H NMR (300 MHz, CDCl} 3) δ6.95 (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]

(2.97 g, 15.0 mmol) of 4,4'-methylene dianiline and 2.00 g (3.7 mmol) of the dianiline obtained in Synthesis Example 1 were dissolved in 31.41 g of N-methyl-2-pyrrolidone 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (1.83 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) were added to γ-butyrolactone (18.69 g) , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 2]

The reaction solution in which p-phenylenediamine (1.62 g, 15.0 mmol) and dianiline obtained in Synthesis Example 1 (2.00 g, 3.7 mmol) were dissolved in N-methyl-2-pyrrolidone (26.62 g) (1.84 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) in γ-butyrolactone (15.84 g) Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 3]

Phenylenediamine (0.81 g, 7.5 mmol) and the dianiline (2.00 g, 3.7 mmol) obtained in Synthesis Example 1 were dissolved in N-methyl-2 -Pyrolidone (29.02 g) was added to a solution of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.83 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) was dissolved in γ-butyrolactone (17.26 g) slowly dropwise over 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 4]

Phenylenediamine (0.81 g, 7.5 mmol) and the dianiline (2.00 g, 3.7 mmol) obtained in Synthesis Example 1 were dissolved in N-methyl-2 (2.10 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) were dissolved in pyrrolidone (29.02 g) at room temperature, Is slowly added dropwise to the reaction solution in γ-butyrolactone (17.82 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 5]

(2.85 g, 14.4 mmol) of 4,4'-methylene dianiline and 2.00 g (3.6 mmol) of the dianiline obtained in the above Synthesis Example 2 were dissolved in 30.45 g of N-methyl-2-pyrrolidone (1.76 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were added to γ-butyrolactone (18.12 g) while maintaining the temperature at room temperature, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 6]

The reaction solution in which p-phenylenediamine (1.55 g, 14.4 mmol) and dianiline (2.00 g, 3.6 mmol) obtained in Synthesis Example 2 were dissolved in N-methyl-2-pyrrolidone (25.85 g) (1.76 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were dissolved in? -Butyrolactone (15.38 g) Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 7]

Phenylenediamine (0.78 g, 7.2 mmol) and the dianiline (2.00 g, 3.6 mmol) obtained in Synthesis Example 2 were dissolved in N-methyl-2 (1.76 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (28.15 g) 9.0 mmol) was dissolved in? -Butyrolactone (16.75 g) and slowly added dropwise to the reaction solution for 2 hours, followed by reaction for 6 hours to obtain a polyamic acid solution.

[Example 8]

Phenylenediamine (0.78 g, 7.2 mmol) and the dianiline (2.00 g, 3.6 mmol) obtained in Synthesis Example 2 were dissolved in N-methyl-2 (2.01 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (28.15 g) Is slowly added dropwise to the reaction solution which is dissolved in? -Butyrolactone (17.28 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 9]

(3.65 g, 18.4 mmol) of 4,4'-methylene dianiline and 2.00 g (4.6 mmol) of the aniline obtained in Synthesis Example 3 were dissolved in 37.01 g of N-methyl-2-pyrrolidone 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (2.26 g, 11.5 mmol) and pyromellitic dianhydride (2.51 g, 11.5 mmol) were added to γ-butyrolactone (22.02 g) , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 10]

The reaction solution in which p-phenylenediamine (1.99 g, 18.4 mmol) and dianiline (2.00 g, 4.6 mmol) obtained in Synthesis Example 3 were dissolved in N-methyl-2-pyrrolidone (31.12 g) (2.26 g, 11.5 mmol) and pyromellitic dianhydride (2.51 g, 11.5 mmol) were dissolved in? -Butyrolactone (18.51 g), and the reaction was carried out by dissolving 1,2,3,4-cyclobutanetetracarboxylic dianhydride Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 11]

(1.800 g, 9.2 mmol), p-phenylenediamine (1.00 g, 9.2 mmol) and the dianiline (2.00 g, 4.6 mmol) obtained in the above Synthesis Example 3 were dissolved in N-methyl-2 (34.07 g) was added to a solution of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.26 g, 11.5 mmol) and pyromellitic dianhydride (2.51 g, 11.5 mmol) was dissolved in γ-butyrolactone (20.27 g) and slowly added dropwise to the reaction solution for 2 hours. The reaction was carried out for 6 hours to obtain a polyamic acid solution.

[Example 12]

(1.800 g, 9.2 mmol), p-phenylenediamine (1.00 g, 9.2 mmol) and the dianiline (2.00 g, 4.6 mmol) obtained in the above Synthesis Example 3 were dissolved in N-methyl-2 (2.5.07 g, 11.5 mmol) and pyromellitic dianhydride (2.51 g, 11.5 mmol) were added to the reaction solution, which was dissolved in pyridine (34.07 g) Is slowly added dropwise to the reaction solution which is dissolved in? -Butyrolactone (20.95 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 13]

(3.00 g, 15.1 mmol) of 4,4'-methylene dianiline and 2.00 g (3.8 mmol) of the dianiline obtained in Synthesis Example 4 were dissolved in 31.69 g of N-methyl-2-pyrrolidone 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (1.86 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were added to γ-butyrolactone (18.85 g) , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 14]

The reaction solution in which p-phenylenediamine (1.64 g, 15.1 mmol) and dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 4 were dissolved in N-methyl-2-pyrrolidone (26.84 g) (1.86 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were dissolved in γ-butyrolactone (15.97 g) Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 15]

Phenylenediamine (0.82 g, 7.6 mmol) and the dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 4 were dissolved in N-methyl-2 (1.86 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were added to the reaction solution, which was dissolved in tetrahydrofuran-pyrrolidone (29.27 g) 9.5 mmol) was dissolved in γ-butyrolactone (17.41 g) slowly dropwise over 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 16]

Phenylenediamine (0.82 g, 7.6 mmol) and the dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 4 were dissolved in N-methyl-2 (2.12 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (29.27 g) Is slowly added dropwise to the reaction solution in which γ-butyrolactone (17.97 g) dissolves for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 17]

(2.98 g, 15.0 mmol) of 4,4'-methylene dianiline and 2.00 g (3.8 mmol) of the dianiline obtained in the above Synthesis Example 5 were dissolved in 31.50 g of N-methyl-2-pyrrolidone 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (1.84 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4 mmol) were added to γ-butyrolactone (18.74 g) , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 18]

The reaction solution in which p-phenylenediamine (1.62 g, 15.0 mmol) and dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 5 were dissolved in N-methyl-2-pyrrolidone (26.69 g) (1.84g, 9.4mmol) and pyromellitic dianhydride (2.05g, 9.4mmol) were dissolved in? -Butyrolactone (15.88g) while reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 19]

Phenylenediamine (0.81 g, 7.5 mmol) and dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 5 were dissolved in N-methyl-2 -Pyrolidone (29.09 g) was added to a solution of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.84 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4 mmol) was dissolved in γ-butyrolactone (17.31 g) and slowly added dropwise to the reaction solution for 2 hours. The reaction mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 20]

Phenylenediamine (0.81 g, 7.5 mmol) and dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 5 were dissolved in N-methyl-2 (2.10 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (29.09 g) Is slowly added dropwise to the reaction solution in γ-butyrolactone (17.86 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 21]

(3.81 g, 19.2 mmol) of 4,4'-methylene dianiline and 2.00 g (4.8 mmol) of the aniline obtained in Synthesis Example 6 were dissolved in 38.30 g of N-methyl-2-pyrrolidone 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (2.35 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were added to γ-butyrolactone (22.78 g) , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 22]

The reaction solution in which p-phenylenediamine (2.08 g, 19.2 mmol) and dianiline (2.00 g, 4.8 mmol) obtained in Synthesis Example 6 were dissolved in N-methyl-2-pyrrolidone (32.15 g) (2.35 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were dissolved in? -Butyrolactone (19.12 g) while reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 23]

Phenylenediamine (1.04 g, 9.6 mmol) and the dianiline (2.00 g, 4.8 mmol) obtained in Synthesis Example 6 were dissolved in N-methyl-2 (2.35 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were added to the reaction solution, which was dissolved in tetrahydrofuran-pyrrolidone (35.22 g) 12.0 mmol) was dissolved in? -Butyrolactone (20.95 g) and slowly added dropwise to the reaction solution for 2 hours, followed by reaction for 6 hours to obtain a polyamic acid solution.

[Example 24]

Phenylenediamine (1.04 g, 9.6 mmol) and the dianiline (2.00 g, 4.8 mmol) obtained in Synthesis Example 6 were dissolved in N-methyl-2 (2.69 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were added to the reaction solution, which was dissolved in pyridine (35.22 g) Is slowly added dropwise to the reaction solution which is dissolved in? -Butyrolactone (21.67 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 25]

(3.75 g, 18.9 mmol) of 4,4'-methylene dianiline and 2.00 g (4.7 mmol) of the aniline obtained in Synthesis Example 7 were dissolved in 37.85 g of N-methyl-2-pyrrolidone (2.32 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were added to γ-butyrolactone (22.51 g) while maintaining the temperature at room temperature, , And the mixture was reacted for 6 hours to obtain a polyamic acid solution.

[Example 26]

The reaction solution in which p-phenylenediamine (2.05 g, 18.9 mmol) and dianiline (2.00 g, 4.7 mmol) obtained in Synthesis Example 7 were dissolved in N-methyl-2-pyrrolidone (31.79 g) (2.32 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were dissolved in? -Butyrolactone (18.91 g) Solution for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 27]

Phenylenediamine (1.02 g, 9.5 mmol) and the dianiline (2.00 g, 4.7 mmol) obtained in Synthesis Example 7 were dissolved in N-methyl-2 (2.32 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were added to the reaction solution, which was dissolved in tetrahydrofuran-pyrrolidone (34.82 g) 11.8 mmol) was slowly added dropwise to the reaction solution in 20.71 g of? -Butyrolactone for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Example 28]

Phenylenediamine (1.02 g, 9.5 mmol) and the dianiline (2.00 g, 4.7 mmol) obtained in Synthesis Example 7 were dissolved in N-methyl-2 (2.65 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (36.00 g) (21.41 g) dissolved in γ-butyrolactone (21.41 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Examples 29 to 56]

The polyamic acid solution obtained in Examples 1 to 28 was dissolved in a solvent in which? -Butyrolactone and butyl cellosolve were mixed to prepare a solution having a concentration of 5% by weight, and the solution was filtered with a filter of 0.1 占 퐉 to prepare a polyimide liquid crystal aligning agent .

[Comparative Example 1]

(1.52 g, 7.7 mmol), p-phenylenediamine (0.83 g, 7.7 mmol) and cholestan-3-ol, 3,5-diaminobenzoate (2.00 g, 3.8 mmol ) Was dissolved in N-methyl-2-pyrrolidone (29.51 g) was added dropwise to a solution of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.88 g, 9.6 mmol) and pyromellitic dianhydride Tic dianhydride (2.09 g, 9.6 mmol) is dissolved in γ-butyrolactone (17.56 g) slowly dropwise over 2 hours and reacted for 6 hours to obtain a polyamic acid solution.

[Comparative Example 2]

(1.52 g, 7.7 mmol), p-phenylenediamine (0.83 g, 7.7 mmol) and cholestan-3-ol, 3,5-diaminobenzoate (2.00 g, 3.8 mmol ) Was dissolved in N-methyl-2-pyrrolidone (30.46 g) was added dropwise to a solution of 2,3,5-cyclotetracarboxylic dianhydride (2.14 g, 9.6 mmol) and pyromellitic dianhydride (2.09 g, 9.6 mmol) was dissolved in? -Butyrolactone (18.12 g) and slowly added dropwise to the reaction solution for 2 hours, followed by reaction for 6 hours to obtain a polyamic acid solution.

[Comparative Examples 3 to 4]

The liquid crystal aligning agents were prepared in the same manner as in the production of the polyamic acid solutions obtained in Comparative Examples 1 and 2,

[Example 57]

1) Formation of polyimide alignment film

The liquid crystal aligning agents obtained in Examples 29 to 56 and Comparative Examples 3 and 4 were applied to a glass substrate on which a transparent conductive film was patterned by a spinner method. After the application, the substrate was prebaked at 100 캜 for 30 minutes and then baked at 250 캜 for 1 hour to obtain a substrate on which a polyimide alignment film having a thickness of 700 Å was formed.

2) Fabrication of liquid crystal display device

The two substrates were opposed to each other with a certain gap (cell gap) without rubbing the orientation film surface of the two substrates on which the liquid crystal alignment film was formed as described above, and the two peripheral portions of the substrate were bonded using a sealing agent, Liquid crystal was injected and filled in the cell gap defined by the liquid crystal cell, and the injection hole was sealed to fabricate the liquid crystal cell. Then, a polarizing plate was bonded to the outer surface of the liquid crystal cell, that is, the other surface of each substrate constituting the liquid crystal cell so that the direction of the polarization axis thereof was orthogonal to obtain a liquid crystal display element. As the sealing agent, a thermosetting resin and an epoxy resin containing aluminum oxide as a spacer were used. The properties of the liquid crystal aligning agent using the polyimide resin prepared in the present invention, such as (1) squareness of the pretilt angle and (2) orientation, were evaluated by the following methods, and the results are shown in Table 1.

① Linear angle of LCD

Was measured by a crystal rotation method using He-Ne laser light according to the method described in T.J. Schffer, et.al., J., Appl., Phys., Vol.19, 2013 (1980).

② liquid crystals

The presence or absence of an abnormal domain in the liquid crystal cell when the voltage was turned on / off on the liquid crystal display device was observed under a microscope, and the case where there was no abnormal domain was judged as "good".

Table 1

Example	Polyamic acid (Example)	Diamine (synthesis example)	Square angle (°)	Pear
29	One	One	4.5	0
30	2	One	4.5	0
31	3	One	4.5	0
32	4	One	4.5	0
33	5	2	89.0	0
34	6	2	89.0	0
35	7	2	89.0	0
36	8	2	89.0	0
37	9	3	1.5	0
38	10	3	1.5	0
39	11	3	1.5	0
40	12	4	1.5	0
41	13	4	89.0	0
42	14	4	89.0	0
43	15	4	89.0	0
44	16	4	89.0	0
45	17	5	89.0	0
46	18	5	89.0	0
47	19	5	89.0	0
48	20	5	89.0	0
49	21	6	89.0	0
50	22	6	89.0	0
51	23	6	89.0	0
52	24	6	89.0	0
53	25	7	89.0	0
54	26	7	89.0	0
55	27	7	89.0	0
56	28	7	89.0	0
Comparative Example
3	One		88.5	X
4	2		88.5	X

Examples 29 to 32 of the polyimide resins using the diamine of Synthesis Example 2 in the above Examples are suitable for the TN mode (4 to 5 占), and the polyimide resins Examples 37 to 40 2 °) is suitable for the IPS mode.

Comparing the characteristics of the examples and the comparative examples, the polyamic acid except for the examples 29 to 32 and 37 to 40 according to the present invention exhibited a VA mode (89 to 90 °) It is possible to confirm that a high pretilt angle is formed at a desired angle.

According to the present invention, it is possible to obtain a liquid crystal aligning agent capable of maximizing the interaction effect between the liquid crystal molecules and the side chains of the polyimide by using the diamine compound, have. And a liquid crystal alignment film formed using the alignment agent and a liquid crystal display element having the liquid crystal alignment film.

Claims (9)

1. A diaminobenzene derivative for vertical alignment represented by the following Formula 1:

   Formula 1

   

   (R ₁ is in the formula (1)

   

   ego,

   X ₁ is an alkyl end group having 12 to 20 carbon atoms when n = 0, and X ₁ is a CH ₂ linking group when n = 1, and n is 0 or 1. X ₂ is -O- or -COO-, -OCO-, -CH2O - a linking group selected _{from, -, - OCH 2 -,} -CF 2 O-, -OCF 2 -, -CH 2 CH 2

   Z ₁ and Z ₂ are independently a single bond,

   

   or

   

   Y ₁ , Y ₂ , Y ₃ and Y ₄ are independently H or F,

   Z ₃ can be selected from alkyl, fluorine, alkoxy, fluoroalkyl, fluoroalkoxy, and a has a value between 0 and 5.)
2. (a) reacting a side chain-type diamine compound of the formula (1) with a tetracarboxylic acid anhydride of the formula (2) and a diamine compound having no side chain of the formula (3) in the presence of a solvent to produce a polyamic acid block copolymer; And

   (b) heat-treating the polyamic acid-based block copolymer in the production step (a) to convert it into polyimide by a dehydration ring-closure reaction; and

   Formula 1

   

   (The definition of the substituent in the above formula (1) is the same as described in claim 1.)

   (2)

   

   (3)

   

   (In the above formulas (2) and (3), A is a tetravalent organic group constituting the tetracyclic acid and R ₂ is a divalent organic group having no side chain group.)
3. 3. The method of claim 2,

   The diamine represented by the above-mentioned general formula (3) is preferably selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, Phenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diamino Diphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9- , 4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'- diaminobiphenyl, 2,2'-dichloro-4,4'- Dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '- (p-phenyleneisopropylidene) bisaniline, 4 Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4 ' -Diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2- trifluoromethyl) phenoxy] -octafluorobiphenyl, di -Aminophenyl) benzidine, 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 1,1-methoxysilylenediamine, Diamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine , Octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.02,7] -undecylenediimethyldiamine, 4,4 ' Aliphatic or alicyclic diamines such as methylene bis (cyclohexylamine) and 1,3-bis (aminomethyl) cyclohexane; Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- 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-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, Aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl) 3-jade Wherein the polyimide resin is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, and polyvinyl alcohol.
4. 3. The method of claim 2,

   Examples of the alicyclic acid dianhydrides represented by Formula 2 include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride Water, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4- 5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene- 2,5,6-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) Cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxy norbornane-2: Dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro- -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] -furan-l, 3,3a, 4,5,9b-hexahydro- -Dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro- 3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl Cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione)

   Examples of the aromatic acid dianhydrides represented by Formula 2 include pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3' 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetra 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, '-Perfluoroisopropylidene diphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) (Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether (triphenylphthalic acid) dianhydride, m-phenylene- Dianhydrides, dianhydrides, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate) Bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2- (Hydroxyphenyl) propane-bis (anhydrotrimellitate), or a mixture thereof. The method for producing a polyimide resin for a vertical alignment agent of a liquid crystal display device according to claim 1,
5. 3. The method of claim 2,

   The solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphoramide, tetramethylene sulfone, p- Wherein the liquid crystal alignment agent is an inert solvent selected from the group consisting of bromophenol, 2-chloro-4-hydroxytoluene, dioxane, tetrahydrofuran (THF), and cyclohexanone. A method for producing a polyimide resin.
6. A polyimide resin for a liquid crystal aligning agent of a liquid crystal display device having a weight average molecular weight of 1,000 to 200,000, which is produced by the production method of claim 2.
7. The method according to claim 6,

   Wherein the side chain length of the polyimide 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.
8. A liquid crystal alignment film produced by using the polyimide resin for a liquid crystal aligning agent of the liquid crystal display device according to claim 6.
9. 9. A liquid crystal display element comprising the liquid crystal alignment film according to claim 8.