WO2012157982A2

WO2012157982A2 - Diamine compound, method for preparing same, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device

Info

Publication number: WO2012157982A2
Application number: PCT/KR2012/003910
Authority: WO
Inventors: 이성규; 최진욱; 안용호; 소상완
Original assignee: 주식회사 동진쎄미켐
Priority date: 2011-05-18
Filing date: 2012-05-17
Publication date: 2012-11-22
Also published as: CN103748068B; CN103748068A; WO2012157982A3; KR101990302B1; TW201247600A; KR20130004069A

Abstract

The present invention relates to an amine compound, a method for preparing same, and a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device, having same. A liquid crystal alignment agent having polyamic acid or polyimide prepared using the amine compound of the present invention enables a liquid crystal alignment film and a liquid crystal display device having an excellent thermal stability even after forming the liquid crystal alignment film, and expressing high alignment and stability even after an ultraviolet ray irradiation.

Description

【Specification】

[Name of invention]

Diamine compound, its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element

Technical Field

This invention relates to a diamine compound, its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element. More specifically, the present invention relates to a diamine compound having a novel structure that can be used as a photoalignment agent, a method for preparing the same, a liquid crystal aligning agent, a liquid crystal alignment layer, and a liquid crystal display device.

This application is subject to the Korean Patent Application No. 10-2011-0047028 filed with the Korea Patent Office on May 18, 2011 and the Korean Patent Application No. 10-2011-0047030 filed with the Korea Patent Office on May 18, 2011. Claiming benefit, the entire contents of which are incorporated herein.

Background Art

Among the constituent materials of the liquid crystal display, the liquid crystal alignment layer is in contact with the liquid crystal molecules and plays a role of uniformly aligning the liquid crystal molecules. The liquid crystal alignment layer is a key material for driving the liquid crystal to uniformly align the liquid crystal in one direction so that the liquid crystal can perform the role of a polarizer of the light. The liquid crystal alignment characteristic of the liquid crystal alignment layer and the electrical characteristics as a thin film are the characteristics of the liquid crystal display. It influences the display quality.

Representative methods for forming the liquid crystal alignment film include inorganic vapor deposition, Langmuir-Blodgett (LB) method, polymer stretching method, rubbing method, and the like, and photo-alignment method and ion beam irradiation method. It is proposed. The most commonly used method is rubbing, which rubs the surface of the substrate with a cloth. The rubbing method is a method in which a glass substrate is rubbed in a predetermined direction with paper, and the long axes of the liquid crystal molecules are aligned and aligned along the rubbing direction. This rubbing method is an orientation method that is most commonly used industrially because it has an advantage of easy orientation processing, which is suitable for mass production, stable orientation, and easy control of pretilt angle. As the material of the alignment film, polyimide having low dielectric constant, high thermal stability, excellent mechanical strength, and excellent process capability is most used. However, various problems or disadvantages have been pointed out in using polyimide as an alignment film material. First, since static electricity can lead to destruction of thin film transistor (TFT) devices, production machines generally include countermeasures against static electricity, but the rubbing method does not provide a complete solution to the static electricity generated during the orientation process. There is this. Second, since dust may be generated in the course of the rubbing process, a cleaning process is required as a subsequent step, which may cause inefficiency in process progress. Third, since the rubbing conditions between the flat part and the step part of the alignment layer having the step part are different from each other, there is a high possibility of uneven alignment fixing force and inclination angle. Fourth, since the rubbing process is performed only in one direction, there is a disadvantage that the production process of the alignment layer including the separated alignment pixels becomes complicated. Finally, in order to uniformly rub a large substrate, special equipment is required.

Therefore, there is a need for a solution to solve various problems, such as the economical, environmentally unfriendly, unstable, and the optical pattern produced in the conventional optical pattern forming process deteriorates the performance of the product.

[Content of invention]

[Problem to solve]

The present invention uses a photo-alignment technology that is a method for aligning the liquid crystal molecules without rubbing to solve the problems of the conventional liquid crystal alignment method, the thermal stability is excellent even after the formation of the alignment film, high orientation and stability even after ultraviolet irradiation It aims at providing the diamine compound for liquid crystal aligning agent manufacture which can be done.

Further, the present invention is to provide a method for producing the diamine compound in the neck ^"enemy.

Moreover, an object of this invention is to provide the liquid crystal aligning agent containing the polyamic acid or polyimide obtained by reacting tetracarboxylic dianhydride to the diamine component containing the said diamine compound. Moreover, an object of this invention is to provide the liquid crystal aligning film formed from the said liquid crystal aligning agent.

Moreover, an object of this invention is to provide the liquid crystal display element provided with the said liquid crystal aligning film.

[Measures of problem]

The present invention provides a diamine compound represented by the following formula (10). [Formula 10]

In addition, the present invention is a diamine compound represented by the following formula (23).

[Formula 23]

In Formula 10 and Formula 23, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. In addition, the present invention provides a liquid crystal alignment comprising a polyamic acid or a polyimide obtained by reacting a tetraamine dianhydride with a diamine component represented by the formula (10) or a diamine component containing the diamine compound represented by the formula (23). Offer

Moreover, this invention provides the liquid crystal aligning film formed from the said liquid crystal aligning agent.

Moreover, this invention provides the liquid crystal display element provided with the said liquid crystal aligning film.

In addition, the present invention comprises the steps of preparing a compound represented by the following formula (9) and a compound represented by the following formula (8) by reacting the compound represented by the formula (8); And

It provides a method for producing a diamine compound represented by the following formula (10) comprising the step of removing the protecting group PG of the compound represented by the formula (9).

[Formula 6]

[Formula 8]

[Formula 9]

In Chemical Formulas 6,8,9 and 10, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl) is a protecting group selected from the group consisting of.

In addition, the present invention comprises the steps of preparing a compound represented by the formula (22) by reacting a compound represented by the formula (12) and a compound represented by the following formula (21); And

It provides a method for producing a diamine compound represented by the formula (23) comprising the step of removing the protecting group PG of the compound represented by the formula (22).

[Formula 12]

[Formula 23]

In Chemical Formulas 12, 21, 22, and 23, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl) is a protecting group selected from the group consisting of.

【Effects of the Invention】

According to the liquid crystal aligning agent comprising a polyamic acid or a polyimide prepared using the diamine compound of the present invention, by using the optical alignment technology which is a method for aligning the liquid crystal molecules without rubbing, it is possible to ensure the safety and economic efficiency of the process progress Can establish an environmentally friendly manufacturing process.

Moreover, even when the diamine compound of this invention is mixed with the other diamine compound for liquid crystal aligning film manufacture, the whole mixture can be photo-aligned. Therefore, other compounds that cannot apply the photoalignment can also perform photoalignment, so that the range of the photoalignment can be widened and the alignment effect can be enhanced.

[Specific contents to carry out invention]

The liquid crystal aligning agent manufactured from the diamine compound of this invention can manufacture a liquid crystal aligning film using the photo-alignment technique which irradiates a polarized ultraviolet-ray (UV) to a polymer film, without a rubbing process.

Photo-alignment technology uses the principle of generating optical reaction and generating optical anisotropy in the film. Therefore, in order to use the photo-alignment control technology of the liquid crystal, it is necessary to use the light having a linear polarization directional, the photoreaction process of the polymer film such as photoisomerization, photopolymerization or photolysis is required, the polarization of the light irradiated with the direction of the liquid crystal molecules Various conditions are required, such as being able to be controlled by direction.

Photoisomerization reaction has the disadvantages of inverse reaction and contamination of liquid crystal layer due to decomposition products in photolysis reaction.In the case of photopolymerization reaction, the initial polyvinyl cinnamate polymer was investigated. Because of the short wavelength, there is a problem in mass production such as the general purpose large exposure apparatus being difficult to use.

Therefore, in recent years, chalcone-based polymers have been studied to increase the wavelength of ultraviolet rays used, and the chalcone-based polymers are absorbed and long-wavelengths compared to poly (vinyl cinnamate) -based polymers. It was also observed that the photopolymerization reaction was effective. The diamine compound of the present invention is a monomer that can be used as a chalcone-based photopolymerization alignment agent, as well as excellent in the pretilt angle, voltage retention and orientation properties as well as photoalignment It is an excellent photopolymerization alignment agent monomer which makes photo-alignment possible even if it is mixed with a difficult thermal polymerization alignment agent monomer.

In general, polyimide resins that have been widely used as photo-alignment agents refer to high heat-resistant resins prepared by condensation of an aromatic tetracarboxylic acid or a derivative thereof and an aromatic diamine or an aromatic diisocyanate, followed by imidization.

The polyimide resin may have various molecular structures depending on the type of monomer used. Generally, pyromellitic dianhydride (PMDA) or nonphthalic anhydride (BPDA) is used as the aromatic tetracarboxylic acid component, and para-phenylenediamine (p-PDA) and meta-phenylenediamine (m) are used as the aromatic diamine component. -PDA), 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 2,2'- bisaminophenylnuclear fullopropane (HFDA),

Metabisaminophenoxydiphenylsulfone (m-BAPS),

Parabisaminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2'-bisamino Phenoxyphenyl propane (BAPP), 2,2'-bisaminophenoxyphenyl nucleofluoropropane (HFBAPP), etc. are used. In general, in the vertical alignment liquid crystal mode, in order to minimize the change in luminance according to the viewing angle, it is necessary to form multiple domains. To this end, a multi-orientation treatment method is required, but since the orientation range cannot be adjusted in micro units by the rubbing orientation method, a method of patterning or forming electrodes on the upper and lower substrates has been mainly used. However, the above two methods require a manufacturing process additionally, and there are disadvantages in that problems occur in electro-optic properties such as response speed and initial light leakage.

In the present invention, the alignment of the liquid crystal molecules in the liquid crystal display device using such a photo-alignment technology, to provide a compound for producing a liquid crystal alignment film that was able to form a pretilt only by UV exposure after the formation of the alignment film.

Certain terms used in the present specification are used for the purpose of describing the present invention in detail to those skilled in the art. It is not intended to be used to limit the scope of the invention described in the claims.

Hereinafter, a diamine compound, its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element are demonstrated in detail this invention with reference to an Example. However, embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Diamine compound and preparation method thereof

The diamine compound of the present invention may be represented by the following formula (10) or formula (23).

[Formula 10]

[Formula 23]

In Formula 10 and Formula 23, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. According to an embodiment of the present invention, in Formula 10 and Formula 23, n is an integer of 1 to 5, R1 to R8 are the same or different from each other, and each independently, may be H or an alkyl group having 1 to 10 carbon atoms. . For example, in Formulas 10 and 23, η may be 1, and R1 to R8 may be Η.

The diamine compound represented by Formula 10 may include the steps of preparing a compound represented by the following Formula 9, and a compound represented by the following Formula 6; And it may be prepared by the step of removing the protecting group PG of the compound represented by the formula (9).

[Formula 6]

[Formula 8]

[Formula 9]

In Chemical Formulas 6,8,9 and 10, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl), DM PM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl) is a protecting group selected from the group consisting of.

For example, when the PG is BOC, more specifically, the diamine compound represented by Chemical Formula 10 may be prepared by performing the following reactions I, II, III, IV and V stepwise.

[Bungungsik I]

Scheme V

In addition, the compound represented by the formula (23) is a compound represented by the following formula (12), and the compound represented by the following formula 21 to produce a compound represented by the following formula (22); And it may be prepared by the step of removing the protecting group PG of the compound represented by the formula (22).

[Formula 12]

[Formula 21]

[Formula 22]

[23]

In Chemical Formulas 12, 21, 22, and 23, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and independently of each other, H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms, or having 1 to 10 carbon atoms. An alkoxy group; PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- It is a protecting group selected from the group consisting of methoxybenzyl), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl).

For example, when the PG is BOC, more specifically, the diamine compound represented by Formula 23 may be prepared by performing the following semi-formulas VI, VII, and VII step by step.

[Banungsik VI]

[Bungungsik VII]

[Bungungsik VIII]

Starting compounds, intermediate compounds, and product compounds used in the synthesis of the diamine compound represented by the formula (10) or (23) of the present invention may be represented by the following formula (1) to (23).

[Formula 2]

[Formula 3

[Formula 6]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 12]

[Formula 13]

[Formula 17]

[Formula 18]

[Formula 21]

[Formula 23]

In Chemical Formulas 1 to 23, n is an integer of 1 to 20, R1 to R8 are the same or different from each other, and each independently, H, CN, N0 ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms or carbon number Alkoxy group of 1 to 10, PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), B OC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn ( benzyl), Carbamate, pB-methoxybenzyl (PMB), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl). .

The diamine compound represented by Chemical Formula 10, or the diamine compound represented by Chemical Formula 23 may include a chalcone structure and react with tetracarboxylic dianhydride to prepare polyamic acid or polyimide. Liquid crystal aligning agent

The present invention provides a liquid crystal aligning agent containing a polyamic acid or polyimide obtained by reacting tetracarboxylic dianhydride to a diamine component containing a diamine compound represented by the following general formula (10). Moreover, this invention provides the liquid crystal aligning agent containing the polyamic acid or polyimide obtained by making tetracarboxylic dianhydride react with the diamine component containing the diamine compound represented by following General formula (23).

[Formula 10]

In Formula 10 and Formula 23, n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. At this time, the "diamine component" includes at least one diamine compound of the present invention represented by the above formula (10) or formula (23), and refers to further including another diamine compound. In particular, the diamine compound represented by the formula (10) or (23) of the present invention can give a photo-orientation by forming a polyamic acid or polyimide by mixing with other diamine compound having no photoactivity. Therefore, the vertical alignment of the liquid crystal can be stabilized.

As a diamine compound which can be used with the diamine compound represented by the said Formula (10) or (23), for example, P-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4, 4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 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) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] nuxafluoropropane, 2,2-bis (4-aminophenyl) Safluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy ) Benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4 -Aminophenyl) polluene, 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 메 4,4'-diaminobiphenyl, l, 4,4 '-(p-phenyl Lenisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) Phenyl] nuclifluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy Octafluorobiphenyl, di (4-aminophenyl) benz ， 1- (4-aminophenyl) -1,3,3-trimethyl-1H-indene-5-amine, 1,1-methaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, Pentamethylenediamine, nucleomethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene nilenediamine, tricyclo [6.2.1.0 ^{2> 7} ]-undecylenedi methyldiamine, 4,4'-methylenebis (cyclonucleosilamine), 1,3- Aliphatic or alicyclic diamines such as bis (aminomethyl) cyclonucleic acid; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine,

5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5- Triazine, 1,4-bis (3-aminopropyl) piperazine, 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-dia Minopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-

1,2-4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6 -Diaminoacridine, bis (4-aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl) -3-octa And at least one diamine compound selected from the group consisting of decyl succinimide.

As tetracarboxylic dianhydride used for synthesize | combining polyamic acid or polyimide in the liquid crystal aligning agent of this invention, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride Water is available.

As a specific example of the said alicyclic tetracarboxylic dianhydride, it is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4- cyclobutane tetracarr, for example. Acid dianhydrides, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride ， 1,2,3,4-tetramethyl-1,2,3,4 ᅳ cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 , 4,5-cyclonucleic acid tetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclonuxyltetracarboxylic 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- Methyl-3-cyclonuxene-1,2-dicarboxylic anhydride, 3,5,6-tricarbonyl-2-carbox Boxynorbornane -2: 3,5: 6- di-anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, l, 3,3a, 4,5,9b- nucleohydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, l, 3,3a, 4,5,9b-nucleohydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b-nucleohydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-nucleohydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-nucleohydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,33,4,5,915-nucleohydro-8-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3 4,5,91) -nucleohydro-8-ethyl-5 (tetra) Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, l, 3,3a, 4,5,9b-nucleohydro-5, 8-Dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxo Tetrahydrofuranyl) -3- Methyl-3-cyclonuxene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabi Cyclo [3.2.1] octane # 2,4-dione-6-spiro-3'- (tetrahydrofuran-2 ', 5'-dione) and the like. As a specific example of the said aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

As a specific example of the said aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, 4,4'- nonphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3, for example , 3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 3,3 ', 4,4'-biphenyl tertetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenyl silanetetracarboxylic dianhydride, 1,2,3,4-furtetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulphur Feed dianhydride ， 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride ， 3 ， 3 ', 4,4'-perfluoroisopropylydenyphthalic acid Anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, P-phenylene-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-nucleic acid di-bis (anhydrotrimellitate), 1,8-octanedi-bis (anhydrotrimellitate), 2, ² -bis ( ⁴ -hydroxyphenyl) propane-bis (anhydrotrimellitate), etc. are mentioned.

A polyamic acid can be obtained by making the said tetracarboxylic dianhydride react with the diamine component containing the amine compound represented by the said Formula (10), or the amine compound represented by the said Formula (23).

The use ratio of the said tetracarboxylic dianhydride and the said diamine component used for the synthesis reaction of the said polyamic acid is about 0.2 to about 2 the acid anhydride group of the said tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the said diamine component. The ratio which becomes equivalent is preferable, More preferably, it is the ratio which becomes about 0.7 to about 1.2 equivalent.

Synthetic reaction of the polyamic acid is preferably in an organic solvent, under temperature conditions of about -20 to about 150 ^° C, more preferably about 0 to about 100 ^° C, preferably about 1 to about 72 hours, more preferably Preferably for about 3 to about 48 hours.

At this time, the organic solvent is not particularly limited as long as it can dissolve the polyamic acid produced. For example, N_methyl_2-pyridone, Ν, Ν- dimethylacetamide, Ν, Ν-dimethyl Amide compounds such as formamide, 3-butoxy-Ν, Ν-dimethylpropanamide, 3-methoxy-Ν, Ν-dimethylpropanamide, 3-nuxyloxy-Ν, Ν-dimethylpropanamide, dimethyl sulfoxide aprotic compounds such as _γ -butyrolactone, tetramethylurea and nuxamethylphosphortriamide; Phenolic compounds, such as m-cresol, xylenol, a phenol, a halogenated phenol, etc. can be illustrated.

On the other hand, in the organic solvent, alcohol, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used in combination without causing precipitation of polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclonucleool, ethylene glycol, propylene glycol, 1,4-butanedi, triethylene glycol, ethylene glycol monomethyl Tere, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclonucleanone, methyl acetate, ethyl acetate, butyl acetate, Methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol -n-propyl ether, ethylene glycol -i-propyl Ether, ethylene glycol -n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorbenzene, 0-dichlorobenzene, nucleic acid, Heptane, Octane, Benzene, Roluene, Xylene, Isoamyl Propionate, Isoamyl Isobutyre There may be mentioned agent, di-isopentyl ether. As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled off under reduced pressure with an evaporator to obtain a polyamic acid. Further, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent, followed by a step of precipitating with a poor solvent or distilling off under reduced pressure with an evaporator once or several times.

The polyimide can be obtained by imidating by dehydrating and closing the obtained polyamic acid.

The dehydration ring closure of the polyamic acid is preferably carried out by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to the solution as necessary. It is performed by the method of heating. The reaction temperature in the method of heating the polyamic acid of (i) is preferably about 50 to about 200 ° C., more preferably about 60 to about 170 ^° C. The reaction time is preferably about 1 to about 8 hours, more preferably about ₃ to about ₅ hours. If the reaction temperature is less than ₅ (rc, the dehydration ring closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ^° C., the molecular weight of the resulting polyimide may be lowered. On the other hand, in the method of adding the dehydrating agent and the dehydrating ring-closure catalyst in the solution of (ii) polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used varies depending on the target imidation ratio, but it is preferable that the amount of the dehydrating agent be about 0.01 to about 20 moles per 1 mole of the amic acid structure of the polyamic acid.

As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, rutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be about 0.01 to about 10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be made higher as the usage-amount of said dehydrating agent and dehydrating ring closure agent increases. As an organic solvent used for dehydration ring reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned.

The reaction temperature of the dehydration ring closure reaction is preferably about 0 to about 18 CTC, more preferably about 10 to about 150 ^° C. The reaction time is preferably about 1 to about 8 hours, more preferably about 3 to about 5 hours. The polyimide obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or the polyimide obtained may be used for manufacture of a liquid crystal aligning agent after a restriction | limiting.

On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be used as it is to manufacture a liquid crystal aligning agent as it is, or may be used to prepare a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, and after isolating the polyimide, the liquid crystal aligning agent. It may be used for the production of or may be used for the production of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of the polyimide can be performed by performing the same operation as mentioned above as a method of isolation and purification of a polyamic acid. The liquid crystal aligning agent of this invention contains the said polyamic acid or the polyimide which dehydrated and closed the polyamic acid, and the additive mix | blended arbitrarily as needed, The said polymer and additive are preferably melt | dissolved in an organic solvent. Examples of the organic solvents that can be used in the liquid crystal aligning agent of the present invention, for example, N- methyl-pyrrolidone to, _γ - butyrolactone, _γ - lactam butyronitrile, Ν, Ν- dimethylformamide, Ν, Ν-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether , Ethylene glycol ethyl ether, ethylene glycol -η- propyl ether, ethylene glycol -i-propyl ether, ethylene glycol -n- butyl ether (butyl cellosolve), ethylene glycol dimethyl ether ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether diethylene glycol diethyl ether, diethylene glycol monomethyl ether diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate diethylene glycol hair Ether acetate, and 3-appendix when -Ν, Ν- dimethylpropanamide 3-methoxy -Ν, Ν- dimethylpropanamide, 3-oxy haeksil -Ν, Ν- dimethylpropanamide.

The solid content (components other than the solvent of the liquid crystal aligning agent) concentration in the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, but is preferably about 1 to about 10 with respect to the median of the entire liquid crystal aligning agent. It may range from ⁰ wt. / _0.

When the solid content concentration is less than 1% by weight, the film thickness formed by applying the liquid crystal aligning agent is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the thickness becomes too large. A favorable liquid crystal aligning film cannot be obtained, the viscosity of a liquid crystal aligning agent will increase, and coating property will fall. Liquid crystal alignment film

An alignment film can be formed by apply | coating and heating the liquid crystal aligning agent of this invention on a base material. The liquid crystal aligning agent can be applied, for example, by a method such as a coater method, a spinner method, a printing method, or an inkjet method, and then a liquid crystal alignment film is formed by heating the coated surface.

After the application of the liquid crystal aligning agent, preliminary heating (pre-baking) may be preferably performed for the purpose of preventing liquid flow of the applied aligning agent. The prebaking temperature is preferably _: about 30 to about 300 ° C, more preferably about 40 to about 200 ° C, particularly preferably about 50 to about 150 ° C.

Thereafter, the solvent may be completely removed, and a firing (post-baking) process may be performed for the purpose of thermally imidizing the polyamic acid. This firing (post-baking) temperature is preferably about 80 to about 300 ° C., more preferably about 120 to about 25 CTC. In this way, the liquid crystal aligning agent containing a polyamic acid is apply | coated, and after application | coating, an organic solvent is removed, the coating film used as a liquid crystal aligning film is formed, and also the dehydration ring closure is advanced by heating, and it can form into a more imidized liquid crystal aligning film. It may be. The film thickness of the liquid crystal alignment film formed is preferably about 0.001 to about 1 um, more preferably about 0.005 to about 0.5 um.

The dried coating surface may be subjected to an alignment treatment by irradiating ultraviolet rays in a wavelength range of about 150 to about 450 nm. In this case, the intensity of the exposure may be irradiated with energy of about 50 mJ / cm ² to about 10 J / cm ² , preferably about 500 mJ / cm ² to about 5 J / cm ² .

After a series of processes by the above-described optical alignment, a liquid crystal alignment film having an excellent alignment stability and excellent thermal stability can be obtained. Liquid crystal display element

This invention provides the liquid crystal display element containing the said liquid crystal aligning film. The liquid crystal display device may be manufactured according to conventional methods known in the art. For example, one of the two substrates on which the liquid crystal alignment layer according to the present invention is formed is coated with an adhesive containing a ball spacer at the end of the substrate, and then One substrate is bonded together to bond cells. Thereafter, the liquid crystal cell may be completed by injecting a liquid crystal into the completed cell and performing heat treatment.

The liquid crystal display element of this invention provided with the said liquid crystal aligning film shows the excellent orientation state, and is excellent in the thermal stability of a liquid crystal alignment state. Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

Preparation of Diamine Compound Example 1

Preparation of Compound of Formula l (When Xn = l, Rl ~ R8 = H, PG = BOC)

[Bungungsik I]

Starting material 4,4,4-trifluorobutan-l-ol (Formula 1) (95.0 g, 0.74 mol) was dissolved in triethylamine (135 ml, 0.97 mol), 1 L of Methylene Chloride and cooled to 0 ° C. To this was added methanesulfonyl chloride (63.0 ml, 62.0 mol) slowly for 30 minutes. The mixture was stirred at 0 to 10 minutes and reacted at room temperature for 2 hours to prepare 4,4,4-trifluorobutylmethanesulfonate (Formula 2). The result of NMR measurement for the compound of Formula 2 is as follows.

1 H NMR (400 MHz, CDC1 ₃ ) δ 4.30 (t, 2H), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m,

2H)

[Bungungsik Π]

4-hydroxyacetophenone (Formula 3) (75.9 g, 0.56 mol ), KOH (55.2 g, 0.84 mol), the ^{4, 4, 4-trifluorobutyl methanesulfonate} (146 g, 0.61 mol), KI (4.60 g compound of formula 2, 0.03 mol) was added to 2 L of methanol and refluxed for 24 hours to prepare 4 '-(4,4,4-trifluorobutoxy) acetophenone (Formula 4).

The result of NMR measurement for the compound of Formula 4 is as follows.

NMR (400 MHz, CDC1 ₃ ) δ 7.95 (d, 2H), 6.91 (d, 2H), 4.10 (t, 2H), 2.56 (s, 3H), 2.32 (m, 2H), 2.09 (m, 2H )

Scheme III

4-formylbenzoic acid (Formula 5) (51.6 g, 0.34 mol), 4 '-(4,4,4-trifluorobutoxy) acetophenone (Formula 4) (84.6 g, 0.34 mol) was added to 2. ² L of ⁸ 0% ethanol After adding 170 ml of 25% NaOH to it, it was reacted at room temperature for 24 hours. Then ¾0 1.5 L was added and cooled to 0 ^° C. HC1 was added until the pH was ² , followed by stirring for 2 hours, thereby preparing a compound of Formula 6. The result of NMR measurement for the compound of Formula 6 is as follows. 1 H NMR (400 MHz, MeOD) δ 8.20 (d, 2H), 8.09 (d, 1H), 8.00 (s, 4H), 7.76 (d,

1H), 7.12 (d, 2H), 4.18 (t, 2H), 2.45 (m, 2H), 1.99 (m, 2H)

[Bungungsik IV]

After dissolving 2,4-dinitrophenylacetic acid (Formula 7) (70.0 g, 0.30 mol) in 700 mL of THF, BH ₃ SMe _{3 (} 39.0 mL, 2.00 mol) was slowly added and refluxed for 3 hours. Thereafter, the reaction was cooled to room temperature, and then 100 mL of 3 N HC1 was added to prepare 2- (2,4-dinitrophenyl) ethanol. Into the autoclave, 2- (2,4-dinitrophenyl) ethanol (64.0 g, 0.30 mol), methanol 1.2 L, 50% wet 10% Pd / C (6.40 g, 10% w / w.) Was added and hydrogen (3 atm) was prepared in a 12:00 hours in the atmosphere based on the reaction ^{2- (2, 4-diaminophenyl)} ethanol. 2- (2,4-diaminophenyl) ethanol (54.0 g, 0.30 mol) was dissolved in 500 mL THF 600 mL I aq-NaHCO _{3 and} then Boc ₂ 0 (165 g, 76 mol) was added slowly at (TC), Thereafter, reaction was carried out at room temperature for 24 hours to prepare a compound of formula 8.

8 compound (60.0 g, 0.17 mol) is dissolved in 1 L Methylene Chloride, to which a compound of formula 3 (83.6 g, 0.22 mol), EDCI (48.9 g, 0.26 mol), DMAP (14.5 g, 0.12 mol), Add DIPEA (119 mL, 0.68 mol) and react for 12 hours at room temperature

9 compound was prepared.

The result of NMR measurement for the compound of Formula 9 is as follows.

1 H NMR (400 MHz, CDC1 ₃ ) δ 8.05 (d, 4H), 7.79 (m, 2H), 7.71 (d, 2H), 7.64 (d, lH), 7.15 (d, lH), 7.04 (b, lH ), 6.97 (d, 2H), 6.50 (b, lH), 4.47 (t, 2H), 4.13 (t, 2H), 3.00 (t, 2H), 2.36 (m, 2H), 2.09 (m, 2H) [Bungungsik V]

The compound of formula 9 (129 g, 0.18 mol) was dissolved in 1.7 L of Methylene Chloride, and 520 mL of TFA was added at 0 ^° C for 1 hour. Then banung and at room temperature for 4 hours, the solvent was removed under reduced pressure, the novel halo hyangje monomer of the invention ^{^{(E) - 2, 4 -diaminophenethyl}} 4- (3-oxo-3- (4- (4, 4,4-trifluorobutoxy) phenyl) prop-l-enyl) benzoate (Formula 10) was prepared.

The result of NMR measurement for the compound of Formula 10 is as follows.

1 H NMR (400 MHz, CDC1 ₃ ) δ 8.06 (m, 4H), 7.82 (d, IH), 7.71 (d, 2H), 7.64 (d, 1 Hz), 6.97 (d, 2H), 6.89 (d, IH ), 6.10 (m, 2H), 4.47 (t, 2H), 4.13 (t, 2H), 3.89 (b, 2H), 3.53 (b, 2H), 2.89 (t, 2H), 2.33 (m, 2H) , 2.11 Preparation of (m, 2H) Diamine Compound Example 2

Preparation of the compound of formula 23fa = l, Rl ~ R8 = H, PG = BOC

Scheme VI

Dissolve starting material 4,4,4-trifluorobutan-l-ol (Formula 1) (95.0 g, 0.74 mol) in triethylamine (135 ml, 0.97 mol), Methylene Chloride (1 L), and methanesulfonyl chloride (0 ° C) 63.0 ml, 0.81 mol) was added slowly over 30 minutes. remind The mixture was stirred at 0 ° C. for 10 minutes and reacted at room temperature for 2 hours to prepare 4,4,4-trifluorobutyl methanesulfonate (Formula 2).

The result of NMR measurement for the compound of Formula 2 is as follows.

2H)

[Bungungsik VII]

4-hydroxyacetophenone (Formula 3) (72.5 g, 0.53 mol) was dissolved in DMF (700 tnL), and 4, ⁴ , ^4- trifluorobutyl methanesulfonate prepared by Banung Formula VI (Formula ² ) (152 g, 0.64 mol), K Compound 4 was prepared by reacting with ₂ CO ₃ (110 g, 0.80 mol) (98.0 g, ⁷⁵ %). Compound 4 ( ⁹ 8.0 g, 0.4 mol) was dissolved in MC / MeOH (2: 1, 1.2 L) and Bu ₄ NBr ₂ (192 g, 0.4 mol) was slowly added at 10 ^° C or below. After reacting for 12 hours to prepare a compound of formula 11 (120 g, 93%). Compound 11 (120 g, 0.4 mol) was added to triethylphosphite (193 mL, 1.11 mol) and refluxed for 4 hours to prepare compound 12 (60 g, 43%).

The result of NMR measurement for the compound of Formula 12 is as follows. NMR (400 MHz, CDC1 ₃ ) δ 8.01 (d, 2H), 6.93 (d, 2H), 4.12 (m, 6H), 3.61 (s _: IH), 3.53 (s, IH), 2.34 (m, 2H ), 2.08 (m, 2H), 1.33 (t, 6H)

Benzophenone (Formula 13) (100 g, 0.55 mol) and KOH (30.8 g, 0.55 mol) were added to acetonitrile (700 mL) and refluxed for 2 hours to obtain a compound of Formula 14 (98.0 g, 87%) was prepared. To a mixed solution of acetonirile (88.0 mL, 1.67 mol), THF (900 mL) in a nitrogen atmosphere at -78 ° C, slowly add BuLi (2.5 M solution in hexane, 480 mL, 1.19 mol) and stir for 3 hours. , Compound 14 (98.0 g, 0.48 mol) and THF (600 mL) were added to the mixture for 3 hours to prepare compound 15 (102 g, 87%). Concentrated sulfuric acid (460 mL) and fuming nitric acid (69.1 mL) were cooled from 0 to -5 ° C to add compound of formula 15 (91.5 g, 0.37 mol), followed by reaction for 5 hours at 10 ° C or less. 16 compound (103 g, 83%) was prepared. Compound 16 (109 g, 0.32 mol) was added to ⁵⁰ % H ₂ SO ₄ (2 L, v / v), reacted at 150 ° C., and then the temperature was decreased to room temperature. After the reaction was extracted to prepare a compound of formula 17. Dissolve compound 17 (143 g, 0.32 mol) in THF (1 L), slowly add B¾SMe ₂ (90.5 mL, 0.96 mol) at 0 ^° C, and react for 5 hours at 50 ^° C. Prepared.

To the autoclave, add compound of formula 18 (87.0 g, 0.25 mol), methane (1.2 L), 50% wet 10% Pd / C (18.0 g, 20% w / w.) And in a hydrogen (3 atm) atmosphere. The compound of formula 19 was prepared by reacting for 24 hours. Compound 19 (75.0 g, 0.26 mol) was dissolved in THF (1.3 L) / sat-NaHC0 ₃ (1.3 L), and Boc ₂ 0 (172 g, 0.79 mol) was slowly added at 0 ^° C. After reacting for 24 hours at room temperature to give a compound of formula 20 (98.4 g, 77%).

Compound 20 was purified using silica gel column chromatography [EtOAc / MC (1: 1 → 3: 1)]. 4-formylbenzoic acid (91.1 g, 0.61 mol), EDCI (167 g, 0.81 mol), DMAP (12.4 g, 0.11 mol), in a solution of the compound of formula 20 (98.4 g, 0.20 mol) in acetonitrile (1.5 L), DIPEA (87.0 mL, 0.50 mol) was added thereto and reacted at 10 ^° C. or below to prepare a compound of Formula 21 (80.0 g, 53%).

A compound of formula 12 prepared in Scheme VII (82.3 g, 0.22 mol) was dissolved in DMF (650 mL), 60% NaH (8.95 g, 0.23 mol) was dispersed in DMF (520 mL), and reacted for 24 hours. Turned on. A solution of a compound of Formula 21 (64.5 g, 86.0 mmol) in DMF (650 mL) was mixed and reacted at room temperature for 14 hours to prepare a compound of Formula 22 (6 g, 1 g, 65%). Compound 22 was purified using column chromatography [Hexane / EtOAc (2: 1)]. Compound 22 (53.1 g, 44.0 mmol) was dissolved in acetonitile (1.8 L) and TMSI (15.7 mL, 110 mmol) and acetonitrile (260 mL) were added under nitrogen atmosphere, 0 ^° C., and then reacted for 2 hours. The solvent was removed under reduced pressure, and the product was purified using column chromatography (MC / EA = 3: 1) to prepare a compound of formula 23 (30.0 g, 68%).

The result of NMR measurement for the compound of Formula 23 is as follows.

1 H NMR (400 MHz, CDC1 ₃ ) δ 8.00 (dd, 8H), 7.73 (d, 2H), 7.57 (d, 4H), 7.47 (d, 2H), 7.06 (d, 4H), 6.95 (d, 4H) , 6.64 (d, 4H), 4.21 (t, 4H), 4.09 (t, 4H), 3.61 (b, 4H), 2.63 (t, 4H), 2.35 (m, 4H), 2.11 (m, 4H) Next In the following, an example of producing a polyamic acid, a polyimide, a liquid crystal aligning agent, and a liquid crystal aligning film using the diamine compound and carboxylic dianhydride of the present invention is described. In addition, the comparative evaluation is based on the excellent properties of the alignment film using the amine compound of the present invention. Example 1

0.83 g of 4,4-methylene diamine (MDA), 1.17 g of p-phenylene diamine (p-PDA), 1.57 g of cholestan (3,5-diamino benzoate) (CDB), the above polyamine compound prepared 1.03 g of a compound of formula 10 (n = l, R1 ~ R8 = H) of Example 1 was dissolved in 49.0 g of N-methyl-2-pyridone (NMP) under a nitrogen atmosphere, and then maintained at 20 ° C. 4.48 g of 3,5-tricarboxy cyclopentyl acetic anhydride (TCAAH) were added. _G _ W groups butyronitrile was added to the impregnated lactone _(GBL) 32.7 g was banung for 24 hours. After reaction, 36.4 g of g-butyrolactone (GBL), 2.73 g of N-methyl-2-pyrrolidone (NMP), and 51.8 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent A. . (Viscosity 13 cP, 25 ° C.) Example 2

0.75 g of 4,4-methylene diamine (MDA), 0.99 g of p-phenylene diamine (p-PDA), 2.09 g of cholestanol (3,5-diamino benzoate) (CDB), preparation of the diamine compound 1.54 g of a compound of formula 10 (n = l, R1 ~ R8 = H) of Example 1 was dissolved in 53.2 g of N-methyl-2-pyridone (NMP) under a nitrogen atmosphere, and then maintained at 20 ° C. 3,5- 4.48 g of tricarboxy cyclopentyl acetic anhydride (TCAAH) was added. Here _g _ butyronitrile was added to the lactone _(GBL) to 35.5 g and banung vigorously for 24 hours. After the reaction, 39.4 g of g-butyrolactone (GBL), 2.96 g of N-methyl-2-pyridone (NMP) and 56.2 g of butyl salosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent B. . (Viscosity 10 cP, 25 ° C) Example 3

4,4-methylene diamine (MDA) 0.63 g, p-phenylene diamine (p-PDA) 0.84 g, cholestanol (3,5-diamino benzoate) (CDB) 2.61 g, the above diamine compound prepared 2.05 g of the compound of Formula 10 (n == l, R1 to R8 = H) of Example 1 was dissolved in 57.3 g of N-methyl-2-pyridone (NMP) under a nitrogen atmosphere, and then maintained at 20 ^° C. 4.48 g of 2,3,5-tricarboxy cyclopentyl acetic anhydride (TCAAH) was added. Here _g _ butyronitrile was added to the lactone (GBL) to 38.2 g and banung vigorously for 24 hours. After reaction, 42.4 g of g-butyrolactone (GBL), 3.19 g of N-methyl- 2-pyridone (NMP), and 60.5 g of butyl cellosolves (BC) were added, and 5 wt% liquid crystal aligning agent C was obtained. (Viscosity 7 cP, 25 ° C) Example 4

0.83 g of 4,4-methylene diamine (MDA), 1.17 g of p-phenylene diamine (p-PDA), 1.57 g of cholestanol (3,5-diamino benzoate) (CDB), the diamine compound was produced. 2.01 g of the compound of formula 23 (n = l, R1 to R8 = H) of Example 2 was dissolved in 54.3 g of N-methyl-2-pyridone (NMP) under a nitrogen atmosphere, and then maintained at 20 ° C. 4.48 g of 3,5-tricarboxy cyclopentyl acetic anhydride (TCAAH) was added. To this was added 32.2 g of g-butyrolactone (GBL) and reacted for 24 hours. After reaction, 44.2 g of g-butyrolactone (GBL), 3.02 g of N-methyl _ ² -pyrrolidone (NMP) and 57.3 g of butyl cellosolve (BC) were added to obtain 5 wt% liquid crystal aligning agent D. . (Viscosity 10 cP, 25 ° C) Example 5 0.75 g of 4,4-methylene diamine (MDA), 0.99 g of p-phenylenediamine (p-PDA), 2.09 g of cholestanol (3,5-diamino benzoate) (CDB), said diamine compound 3.02 g of the compound of formula 23 (n = l, R1 to R8 = H) of Preparation Example 2 was dissolved in 61.2 g of N-methyl-2-pyridone (NMP) under a nitrogen atmosphere, and then maintained at 20 ^° C. 4.48 g of 2,3,5-tricarboxy cyclopentyl acetic anhydride (TCAAH) was added. To this was added 40.8 g of g-butyrolactone (GBL) and reacted for 24 hours. After the reaction, 45.3 g of g-butyrolactone (GBL), 3.40 g of N-methyl-2-pyridone (NMP) and 64.6 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent E. (Viscosity 9 cP, 25 ^° C) Example 6

4,4-methylene diamine (MDA) 0.50 g, p-phenylene diamine (p-PDA) 0.68 g, cholestanol (3,5-diamino benzoate) (CDB) 2.10 g, the above diamine compound preparation 3.23 g of a compound of Formula 23 (n = l, R1 to R8 = H) of Example 2 were dissolved in 54.6 g of N-methyl-2-pyridone (NMP) under a nitrogen atmosphere, and then maintained at 20 ^° C. 3.60 g of 3,5-tricarboxy cyclopentyl acetic anhydride (TCAAH) was added. To this was added 36.4 g of g-butyrolactone (GBL) and reacted for 24 hours. After the reaction, 40.4 g of g-butyrolactone (GBL), 3.03 g of N-methyl-2-pyridone (NMP) and 57.6 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent F. (Viscosity 7 cP, 25 ^° C) Comparative Example 1

Under methylenedioxy amine (MDA) 0.75 g, P- phenylenediamine (p-PDA) 1.02 g, Collet Stan-ol (3,5-di-amino-benzo on site) (CDB), 5.56 g nitrogen atmosphere ^{^4,4} It was dissolved in 69.0 g of N-methyl-2-pyridone (NMP) and then 5.40 g of 2,3,5-tricarboxy cyclopentyl acetic anhydride (TCAAH) was added while maintaining 20 ^° C. To this was added 46.0 g of g-butyrolactone (GBL) and reacted for 24 hours. After the reaction, 97.15 g of g-butyrolactone (GBL), 72.9 g of N-methyl-2-pyridone (NMP), and 72.9 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent G. (Viscosity 12 cP, 25 ° C) Preparation of liquid crystal aligning film and liquid crystal cell

The liquid crystal aligning agents A-G obtained by the said method were filtered using the filter of 1 micrometer of pore diameters. This liquid crystal aligning agent A to G using a spinner on a transparent conductive film containing an ITO film provided on one surface of a glass substrate using a spinner, rotation time 10 rpm, rotation time 1800 rpm, rotation time 20 seconds It was applied in two steps, and 60 seconds of pre cure at 180 ° C, the main cure for 20 minutes at 210 ^° C to remove the solvent, to form a coating film.

Thereafter, the substrate was exposed for 30 seconds at an intensity of 300 mJ / cm ² and 10 mW using an exposure machine to prepare two (pair) substrates having a liquid crystal alignment film. Subsequently, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 4 um was applied to each of the outer edges of the substrate having the liquid crystal alignment film of the substrate having the pair of liquid crystal alignment films, and then overlapped and pressed so that the liquid crystal alignment film faces each other. , The adhesive was cured. Subsequently, after layering nematic liquid crystals (n _e 1.5601, no 1.4780) between the liquid crystal injection hole and the substrate, the liquid crystal injection hole was sealed with an acrylic photocuring adhesive to manufacture a liquid crystal display device.

Experimental Example

Evaluation of Physical Properties of Liquid Crystal Sal

Assessment Methods

1. Viscosity

Kinematic viscosity was measured using a cannon viscometer at 25 ^° C, specific gravity was measured with a hydrometer, and the viscosity was calculated by multiplying two values. 2. Pretilt angle

It was measured by crystallographic method using He-Ne ray light according to the method described in TJ Schffer, et.al., J., Appl., Phys., Vol. 19, 2013 (1980). .

3. Orientation of Liquid Crystal The presence or absence of an abnormal domain in the liquid crystal display element when voltage was turned on or off in the liquid crystal display element was observed under a microscope, and it was judged that the case where there was no abnormal domain was good. 4. Voltage retention

After applying a voltage of 5 V to the liquid crystal display element for 60 microseconds, the voltage retention after 16.67 milliseconds from the release of the application was measured. Physical property evaluation results of the liquid crystal display device manufactured by Examples and Comparative Examples of the present invention are shown in Table 1 below. Referring to Table 1, it can be seen that the post-exposure orientations of Examples 1 to 6 are remarkably superior to those of Comparative Examples.

[Table 1] Comparison of characteristics of liquid crystal cell

Examples and Comparative Examples of the present invention The liquid crystal alignment photo is shown in Table 2 below.

Referring to Table 2 below, in the photographs after the exposure of Examples 1 to 6, the domain is not seen, but in the case of the comparative example, the difference between the domains before and after the exposure is not seen so much, and it can be seen that the defect. [Table 2] Liquid crystal alignment photograph

Claims

[Patent Claims]

[Claim 1]

Diamine compounds represented by the formula (10)

[Formula 10]

In Chemical Formula 10,

η is an integer from 1 to 20;

R1 to R8 are the same as or different from each other, and are each independently Η, CN, NO ₂ , CF ₃ , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[Claim 2]

The compound of claim 1, wherein n is an integer from 1 to 5; Ri to R ₈ are the same or different from each other, and each independently, H or a diamine compound which is an alkyl group having 1 to 10 carbon atoms.

[Claim 3]

Diamine compounds represented by the following formula (23):

[Formula 23]

In Chemical Formula 23,

n is an integer from 1 to 20;

R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[Claim 4]

The compound of claim 3, wherein n is an integer from 1 to 5; R1 to R8 are the same as or different from each other, and each independently, a diamine compound which is H or an alkyl group having 1 to 10 carbon atoms.

[Claim 5]

Liquid crystal aligning agent containing the polyamic acid or polyimide obtained by making tetracarboxylic dianhydride react with the diamine component containing the diamine compound represented by following formula (10):

[Formula 10]

In Chemical Formula 10,

n is an integer from 1 to 20;

R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[Claim 6]

The liquid crystal aligning agent containing the polyamic acid or the plimide obtained by making tetracarboxylic dianhydride react with the diamine component containing the diamine compound represented by following General formula (23):

[Chemistry 2 ³ ]

In Chemical Formula 23 n is an integer from 1 to 20;

R1 to R8 are the same as or different from each other, and each independently, H, CN,

N0 ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[Claim 7]

The diamine component according to claim 5 or 6, wherein the diamine component is P-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4, 4'-diaminodiphenylsulfide, 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 )-1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3 '-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] nucleated fluoropropane, 2,2-bis (4-aminophenyl) nucleated fluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Sulfones, 1,4-bis (4 -Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydro Anthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'- Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diami i-5,5'-dimethoxy biphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2 '-Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] nucleofluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, di (4-aminophenyl) benzidine, 1- (4-aminophenyl) ᅳ 1,3, 3-trimethyl-1H-indene-5-amine, 1,1-methac Relenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, nucleamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclonucleic acid, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ² ' ⁷ ]- Aliphatic or alicyclic diamines such as undecylenedi methyldiamine, 4,4'-methylenebis (cyclonuxylamine), and 1,3-bis (aminomethyl) cyclonucleic acid; 2,3-diaminopyridine ， 2,6-diaminopyridine ， 3,4-diaminopyridine ， 2,4-diaminopyrimidine _: 5,6-diamino-2,3-diaminopyri Lazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3- Aminopropyl) piperazine, 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-I, ³ , ⁵ -triazine , ^{^{4,6-diamino-_}} ^2-vinyl -S- triazine, ^2, ^{^{4-di-amino-5-phenylthio}} triazole, 2,6-diamino-purine, 5,6-diamino-1,3- Methyluracil, 3,5-diamino- 1,2,4-triazole, 6,9-diamino-2-ethoxy acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1 , 4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenyla At least one diamine selected from the group consisting of 1- (3,5-diaminophenyl) -3-decylsuccinimide and 1- (3,5-diaminophenyl) -3-octadecylsuccinimide The liquid crystal aligning agent containing a compound further.

[Claim 8]

The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 5-7. [Claim 9]

The liquid crystal display element provided with the liquid crystal aligning film of Claim 8.

[Claim 10]

Preparing a compound represented by the following Formula 9 by reacting the compound represented by the following Formula 6 with the compound represented by the following Formula 8; And a method for preparing a diamine compound represented by the following Chemical Formula 10, comprising removing the protecting group PG of the compound represented by the following Chemical Formula 9:

[Formula 6]

[Formula 8]

[Formula 9]

In Chemical Formulas 6, 8, 9 and 10,

n is an integer from 1 to 20;

R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms;

PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Protecting group selected from the group consisting of Bn (benzyl), Carbamate, pB-methoxybenzyl (PMB), DMPM (3,4-dimethoxybenzyl), p-methoxypheyl (PMP), Ts (tosyl), and Ns (nosyl) ° 1.

[Claim 111]

Preparing a compound represented by the following Formula 22 by reacting the compound represented by the following Formula 12 with the compound represented by the following Formula 21; And removing the protecting group PG of the compound represented by the following Chemical Formula 22.

[Formula 12]

[Formula 21]

[Formula 22]

N is an integer of 1 to 20 in Formulas 12, 21, ² 2 and 23; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO ₂ , CF ₃ , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;

PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl) is, DMPM (3, 4-dimethoxybenzyl ), PMP (p-methoxypheyl), Ts (tosyl), and the protecting group is selected from the group consisting of Ns (nosyl) (protecting group) 0].