KR101990302B1 - Diamine Compound, Method for Preparing the same, Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film and Liquid Crystal Display Device - Google Patents

Abstract

[화학식 23]

상기 화학식 10 및 화학식 23에서, n은 1 내지 20의 정수이고; R1 내지 R8은 서로 동일하거나 상이하고 각각 독립적으로, H, CN, NO₂, CF₃, 할로겐, 탄소수 1 내지 10의 알킬기 또는 탄소수 1 내지 10의 알콕시기이다.The present invention relates to an amine compound represented by the following general formula (10) or (23), a process for producing the same, a liquid crystal aligning agent containing the same, a liquid crystal alignment film and a liquid crystal display device. According to the liquid crystal aligning agent comprising a polyamic acid or polyimide produced by using the amine compound according to the present invention, it is possible to provide a liquid crystal alignment film which is excellent in thermal stability even after formation of a liquid crystal alignment film and can exhibit high orientation and stability even after ultraviolet irradiation A liquid crystal display element can be provided.
[Chemical formula 10]

(23)

In the formulas (10) and (23), n is an integer of 1 to 20; R 1 to R 8 are the same or different from each other and each independently represents 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.

Description

(Diamine Compound, Method for Preparing the Same, Liquid Crystal Alignment Film, and Liquid Crystal Display Device)

The present invention relates to a diamine compound, a process for producing the same, a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device. More particularly, the present invention relates to a diamine compound having a novel structure which can be used as a photo-dispersing agent, a process for producing the same, a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device.

Among the constituent materials of the liquid crystal display, the liquid crystal alignment film is in contact with the liquid crystal molecules and plays a role of uniformly orienting the liquid crystal molecules. The liquid crystal alignment layer is a key material of liquid crystal driving that uniformly aligns the liquid crystal in one direction so that the liquid crystal can perform well as a light switch of polarized light. The liquid crystal alignment characteristic of the liquid crystal alignment layer and the electrical characteristics as a thin film are as follows. It affects display quality.

Representative methods for forming a liquid crystal alignment layer include a gradient deposition method of an inorganic material, a Langmuir-Blodgett (LB) method, a polymeric stretching method, and a rubbing method. As a new alignment method, a photo alignment method, Has been proposed. Among these, the most commonly used method is a rubbing method in which the substrate surface is rubbed with a cloth. The rubbing method is a method in which when the glass substrate is rubbed with paper in a certain direction, the long axes of the liquid crystal molecules are aligned and aligned in accordance with the rubbing direction. Such a rubbing method is an orientation method that is most widely used industrially because it is easy to orientate and is suitable for mass production, has stable orientation, and has advantages of easy control of pretilt angle.

As the material of the orientation film, polyimide having a low dielectric constant, high thermal stability, excellent mechanical strength and excellent processability is most widely used. However, various problems or disadvantages are pointed out in using polyimide as an alignment film material as follows. First, production machines generally include countermeasures against static electricity, because static electricity can cause destruction of thin film transistor (TFT) devices, but the rubbing method does not provide a complete solution to the static electricity generated in the orientation process . Secondly, dust may be generated in the course of the orientation according to the rubbing method. Therefore, a cleaning process is required as a subsequent step, which may cause inefficiency in process progress. Third, since the rubbing conditions of the plane portion and the step portion of the alignment layer having stepped portions are different from each other, there is a high possibility that the alignment fixation force and the inclination angle are uneven. 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 is complicated. Finally, there is a disadvantage that special equipments are required to uniformly rub large substrates.

Therefore, there is a need for measures to solve various problems such as non-economic property of the conventional optical pattern forming process, environmental non-affinity, unstability, and the produced optical pattern deteriorating the performance of the product.

In order to solve the problems of the conventional liquid crystal alignment method, the present invention uses a photo-alignment technique, which is a method for aligning liquid crystal molecules without rubbing, and exhibits excellent thermal stability even after formation of an orientation film and exhibits high orientation and stability even after ultraviolet irradiation And to provide a diamine compound for use in the production of a liquid crystal aligning agent.

It is another object of the present invention to provide a process for producing the diamine compound.

Another object of the present invention is to provide a liquid crystal aligning agent comprising a polyamic acid or polyimide obtained by reacting a diamine component containing the diamine compound with a tetracarboxylic dianhydride.

It is another object of the present invention to provide a liquid crystal alignment film formed from the liquid crystal aligning agent.

It is another object of the present invention to provide a liquid crystal display element having the liquid crystal alignment film.

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

[Chemical formula 10]

The present invention also provides a diamine compound represented by the following formula (23).

(23)

In the formulas (10) and (23), n is an integer of 1 to 20; R 1 to R 8 are the same or different from each other and each independently represents 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.

The present invention also relates to a liquid crystal alignment layer comprising a polyamic acid or polyimide obtained by reacting a diamine compound represented by the above formula (10) or a diamine component containing the diamine compound represented by the above formula (23) with a tetracarboxylic dianhydride .

The present invention also provides a liquid crystal alignment layer formed from the liquid crystal aligning agent.

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

The present invention also relates to a process for preparing a compound represented by the following formula (9) by reacting a compound represented by the following formula (6) with a compound represented by the following formula (8) And

There is provided a process for preparing a diamine compound represented by the following general formula (10), which comprises the step of removing a protecting group PG of a compound represented by the following general formula (9).

[Chemical Formula 6]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

N is an integer of 1 to 20; R 1 to R 8 are the same or different and 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 a carbodiimide compound which is selected from the group consisting of Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl) Ac Acetyl Bz Benzyl, Carbamate, methoxybenzyl), 3,4-dimethoxybenzyl (DMPM), p-methoxypheyl (PMP), Ts (tosyl), and Ns (nosyl).

The present invention also relates to a process for preparing a compound represented by the following formula (22) by reacting a compound represented by the following formula (12) with a compound represented by the following formula (21) And removing the protecting group PG of the compound represented by the following formula (22).

[Chemical Formula 12]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

In the above formulas (12), (21), (22) and (23), n is an integer of 1 to 20; R 1 to R 8 are the same or different and 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 a carbodiimide compound which is selected from the group consisting of Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl) Ac Acetyl Bz Benzyl, Carbamate, methoxybenzyl), 3,4-dimethoxybenzyl (DMPM), p-methoxypheyl (PMP), Ts (tosyl), and Ns (nosyl).

According to the liquid crystal aligning agent comprising the polyamic acid or polyimide produced by using the diamine compound of the present invention, the optical alignment technique which is a method for aligning the liquid crystal molecules without rubbing is used, And an environmentally friendly manufacturing process can be established.

Also, when the diamine compound of the present invention is mixed with another diamine compound for producing a liquid crystal alignment film, the entire mixture can be broadly oriented. Therefore, other compounds that can not be subjected to photo-alignment can also be photo-aligned, so that the range of photo-alignment can be widened and the orientation effect can be enhanced.

The liquid crystal aligning agent prepared from the diamine compound of the present invention can produce a liquid crystal alignment film by using a photo-alignment technique of irradiating polarized ultraviolet (UV) to the polymer film without rubbing treatment.

The photo-alignment technique utilizes the principle of causing optical reaction to generate optical anisotropy in the film. Therefore, in order to utilize the optical alignment control technique of the liquid crystal, it is necessary to use light having a directivity of linear polarization, and a photoreaction process of a polymer film such as photoisomerization, photopolymerization or photolysis is required, It is required to be able to be controlled by a direction.

The photoisomerization reaction has disadvantages such as the effect of the reverse reaction and the contamination of the liquid crystal layer due to decomposition products in the photolysis reaction. In the photopolymerization reaction, an initial poly (vinyl cinnamate) polymer was examined, Since the wavelength of ultraviolet rays is short, there is a problem in mass production such as difficulty in using a general-purpose large-sized exposure apparatus.

Recently, a chalcone-based polymer has been investigated in order to make the wavelength of ultraviolet light to be used longer. In comparison with a poly (vinyl cinnamate) -based polymer, a chalcone-based polymer has a long absorption wavelength, It was also observed that the photopolymerization reaction was efficient. The diamine compound of the present invention is a monomer that can be used as a chalcone-based photopolymerization aligning agent and has excellent light-polymerizing orientation that enables excellent optical alignment even when mixed with a thermopolymerization-regulating monomer which is excellent in the angle of incidence, voltage retention rate and orientation, Monomer.

In general, a polyimide resin widely used as a light distributing agent refers to a high heat resistant resin produced by condensation polymerization of an aromatic tetracarboxylic acid or its derivative with an aromatic diamine or an aromatic diisocyanate followed by imidization.

The polyimide resin may have various molecular structures depending on the kind of the monomers used. In general, pyromellitic acid dianhydride (PMDA) or biphthalic anhydride (BPDA) is used as the aromatic tetracarboxylic acid component, and para-phenylenediamine (p-PDA), meta-phenylenediamine -PDA), 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 2,2'-bisaminophenylhexafluoropropane (HFDA), methabisaminophenoxydi (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), and 1,3-bisaminophenoxybenzene (TPE-R) , 2,2'-bisaminophenoxyphenylpropane (BAPP), and 2,2'-bisaminophenoxyphenylhexafluoropropane (HFBAPP).

Generally, in the Vertical Alignment Liquid Crystal Mode, multiple domains must be formed in order to minimize a change in luminance depending on a viewing angle. In order to accomplish this, a multi-directional processing method is required. However, in the rubbing alignment method, since the alignment range can not be controlled in units of micrometers, a method of patterning or forming protrusions on the upper and lower substrates is mainly used. However, the above-described two methods have a disadvantage in that a manufacturing process is additionally required and problems occur in electrooptical characteristics such as response speed and initial light leakage.

In the present invention, it is intended to provide a compound for producing a liquid crystal alignment layer capable of forming pre-tilt only by UV exposure after alignment film formation by aligning liquid crystal molecules in a liquid crystal display device using such photo alignment technology.

It is to be understood that the specific terminology used herein is for the purpose of describing the invention in detail, and is not intended to limit the scope of the invention as defined in the claims or the claims.

Hereinafter, the present invention will be described in more detail with reference to examples with reference to a diamine compound, a production method thereof, a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device. However, the embodiments according to the present invention can be modified into 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 invention are provided to more fully describe the present invention to those skilled in the art.

Diamine  Compounds and their preparation

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

[Chemical formula 10]

(23)

In the formulas (10) and (23), n is an integer of 1 to 20; R 1 to R 8 are the same or different from each other and each independently represents 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, n is an integer of 1 to 5, and R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms . For example, in the above formulas (10) and (23), n may be 1 and R 1 to R 8 may be H.

The diamine compound represented by Formula 10 may be prepared by reacting a compound represented by Formula 6 with a compound represented by Formula 8 to prepare a compound represented by Formula 9; And removing the protecting group PG of the compound represented by the following general formula (9).

[Chemical Formula 6]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

N is an integer of 1 to 20; R 1 to R 8 are the same or different and 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 a carbodiimide compound which is selected from the group consisting of Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl) Ac Acetyl Bz Benzyl, Carbamate, methoxybenzyl), 3,4-dimethoxybenzyl (DMPM), p-methoxypheyl (PMP), Ts (tosyl), and Ns (nosyl).

For example, when PG is BOC, more specifically, the diamine compound represented by Formula 10 can be prepared by performing the following Reaction Schemes I, II, III, IV, and V in a stepwise manner.

[Reaction Scheme I]

[Reaction Scheme II]

[Reaction Scheme III]

[Reaction Scheme IV]

[Reaction Scheme V]

Further, the compound represented by Formula 23 may be prepared by reacting a compound represented by Formula 12 with a compound represented by Formula 21 to prepare a compound represented by Formula 22 below. And removing the protecting group PG of the compound represented by the following formula (22).

[Chemical Formula 12]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

In the above formulas (12), (21), (22) and (23), n is an integer of 1 to 20; R 1 to R 8 are the same or different and 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 a carbodiimide compound which is selected from the group consisting of Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl) Ac Acetyl Bz Benzyl, Carbamate, methoxybenzyl), 3,4-dimethoxybenzyl (DMPM), p-methoxypheyl (PMP), Ts (tosyl), and Ns (nosyl).

For example, when the PG is BOC, more specifically, the diamine compound represented by the formula (23) can be prepared by performing the following reaction schemes VI, VII and VII in a stepwise manner.

[Reaction Scheme VI]

[Reaction Scheme VII]

[Reaction Scheme VIII]

The starting compounds, the intermediate compounds and the resulting compounds used in the synthesis of the diamine compounds represented by the formula (10) or (23) of the present invention may be represented by the following formulas (1) to (23).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

 (7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

In the above Chemical Formulas 1 to 23, n is an integer of 1 to 20, and R 1 to R 8 are the same or different and each independently represents H, CN, NO ₂ , CF ₃ , halogen, an alkyl group having 1 to 10 carbon atoms, And PG is an alkoxy group having from 1 to 10 carbon atoms and PG is selected from the group consisting of Cbz (carbobenzyloxy), Moz (p-Methoxybenzylcarbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl) , Carbamate, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (DMPM), p-methoxypheyl (PMP), Ts (tosyl), and Ns (nosyl).

The diamine compound represented by the formula (10) or the diamine compound represented by the formula (23) includes a chalcone structure and can be used for producing a polyamic acid or a polyimide by reacting with a tetracarboxylic dianhydride.

Liquid crystal Orientation agent

The present invention provides a liquid crystal aligning agent comprising a polyamic acid or a polyimide obtained by reacting a diamine component containing a diamine compound represented by the following formula (10) with a tetracarboxylic dianhydride.

The present invention also provides a liquid crystal aligning agent comprising a polyamic acid or polyimide obtained by reacting a diamine component containing a diamine compound represented by the following formula (23) with a tetracarboxylic dianhydride.

[Chemical formula 10]

(23)

In the formulas (10) and (23), n is an integer of 1 to 20; R 1 to R 8 are the same or different from each other and each independently represents 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.

The term "diamine component" means at least one diamine compound of the present invention represented by the above formula (10) or (23), and optionally further includes another diamine compound.

In particular, the diamine compound represented by the above formula (10) or (23) of the present invention can form a polyamic acid or polyimide by mixing with another diamine compound having no photoactive property to impart photo-alignment property. Therefore, the vertical alignment of the liquid crystal can be stabilized.

Examples of the diamine compound that can be used in combination with the diamine compound represented by Formula 10 or Formula 23 include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- 4'-diaminobiphenyl 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) Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2- Aminophenoxy) piperazine (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 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'-diamino-5,5'-dimethoxybiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'- (p-phenyleneisopropylidene) bisaniline, 4,4 '- (m- phenyleneisopropylidene) Bis-aniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino- (4-aminophenyl) benzidine, 1- (4-amino-phenyl) ) -1,3,3-trimethyl-1H-inden-5-amine, 1,1-methoxysilylenediamine, But are not limited to, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2 Alicyclic or alicyclic diamines such as 1, 2, ⁷ ] undecylenedimethyldiamine, 4,4'-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 And at least one diamine compound selected from the group consisting of tetradecylsuccinimide.

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid or polyimide in the liquid crystal aligning agent of the present invention, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride Water can be heard.

Specific examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracar 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-cyclobutane tetracarboxylic 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 acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3- Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane- Tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-fura 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro- 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-hexahydro (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] , 9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3- furanyl) -naphtho [ , 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5- dioxotetrahydrofuranyl) Hexene-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). Specific examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride and the like.

Specific examples of the aromatic tetracarboxylic acid dianhydride 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 Bis (triphenylphthalic acid) dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m- , Diphenyl ether dianhydride, 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 , 2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), and the like.

The polyamic acid can be obtained by reacting the tetracarboxylic dianhydride with an amine compound represented by the formula (10) or an amine compound represented by the formula (23).

The ratio of the tetracarboxylic dianhydride and the diamine component used in the synthesis reaction of the polyamic acid is about 0.2 to about 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride with respect to one equivalent of the amino group of the diamine component , And more preferably from about 0.7 to about 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably about -20 to about 150 캜, more preferably about 0 to about 100 캜, preferably about 1 to about 72 hours, For about 3 to about 48 hours.

The organic solvent is not particularly limited as long as it can dissolve the resulting polyamic acid. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, Amide compounds such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide and 3-hexyloxy- Nonpolar compounds such as butyrolactone, tetramethyl urea, and hexamethylphosphoric triamide; phenol compounds such as m-cresol, xylenol, phenol, halogenated phenol, and the like.

On the other hand, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon or the like which is a poor solvent of polyamic acid can be used in the organic solvent in a range in which polyamic acid to be produced is not precipitated. Specific examples of such a poor solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, Butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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, Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o- Dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether. In this way, a reaction solution obtained by dissolving polyamic acid is obtained. Then, this reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and this precipitate is dried under reduced pressure, or the reaction solution is distilled off under reduced pressure using an evaporator to obtain a polyamic acid. The polyamic acid can be purified by once or several times the step of dissolving the polyamic acid in an organic solvent and then precipitating with a poor solvent or by distillation under reduced pressure using an evaporator.

The obtained polyamic acid is dehydrated and cyclized to imidize the polyimide.

The dehydration ring-closure of the polyamic acid is preferably carried out by a method comprising the steps of (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring- And then heating it. The reaction temperature in the method of heating the polyamic acid of (i) is preferably about 50 to about 200 캜, more preferably about 60 to about 170 캜. 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 50 캜, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered.

 On the other hand, in the method (ii) of adding the dehydrating agent and dehydrating ring-closing catalyst to the solution of the polyamic acid, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably from about 0.01 to about 20 mol based on 1 mol of the amic acid structure of the polyamic acid although it differs depending on the aimed imidization rate.

As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably about 0.01 to about 10 mol per 1 mol of the dehydrating agent used. The imidization rate can be increased as the amount of the dehydrating agent and the dehydrating ring closure agent used is larger. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for use in the synthesis of polyamic acid.

The reaction temperature of the dehydration ring closure reaction is preferably about 0 to about 180 캜, more preferably about 10 to about 150 캜. The reaction time is preferably about 1 to about 8 hours, more preferably about 3 to about 5 hours. The polyimide obtained in the above method (i) can be used as it is for the production of a liquid crystal aligning agent, or after the obtained polyimide is purified, it can be used for the production of a liquid crystal aligning agent.

On the other hand, in the above method (ii), a reaction solution containing polyimide is obtained. This reaction solution can be used as it is for the production of a liquid crystal aligning agent, or after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, it can be used for the production of a liquid crystal aligning agent or after the polyimide is isolated, Or may be used in the production of a liquid crystal aligning agent after purification of the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. Isolation and purification of polyimide can be carried out by carrying out the same operation as described above as a method for isolation and purification of polyamic acid.

The liquid crystal aligning agent of the present invention comprises polyimic acid or a polyimide obtained by dehydrocondylating the polyamic acid and optional additives optionally blended, wherein the polymer and the additive are preferably dissolved in an organic solvent.

Examples of the organic solvent usable in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, , Ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Agent, and the like can be mentioned 3-butoxy -N, N- dimethylpropanamide, 3-methoxy -N, N- dimethylpropanamide, 3-hexyloxy -N, N- dimethylpropanamide.

The concentration of the solid component (the component other than the solvent of the liquid crystal aligning agent) in the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, etc., but is preferably about 1 to about 10 % ≪ / RTI > by weight.

When the solid concentration is less than 1% by weight, a film thickness formed by applying the liquid crystal aligning agent becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, A good liquid crystal alignment film can not be obtained, and the viscosity of the liquid crystal aligning agent is increased and the coating property is lowered.

Liquid crystal alignment film

A liquid crystal alignment film can be formed by applying the liquid crystal aligning agent of the present invention on a substrate and heating it.

The liquid crystal aligning agent can be applied by, for example, a roll coater method, a spinner method, a printing method, or an ink jet method, and then the coated surface is heated to form a liquid crystal alignment film.

After the application of the liquid crystal aligning agent, preheating (prebaking) can be preferably carried out for the purpose of preventing the flow of the applied aligning agent or the like. The prebaking temperature is preferably about 30 to about 300 캜, more preferably about 40 to about 200 캜, and particularly preferably about 50 to about 150 캜.

Thereafter, a baking (post-baking) process can be performed for the purpose of completely removing the solvent and thermally imidizing the polyamic acid. The firing (post bake) temperature is preferably about 80 to about 300 캜, and more preferably about 120 to about 250 캜. Thus, a coating film to be a liquid crystal alignment film is formed by applying a liquid crystal aligning agent containing polyamic acid, removing the organic solvent after coating, and heating to proceed dehydration ring closure to form a more imaged liquid crystal alignment film It is possible. The film thickness of the liquid crystal alignment film to be formed is preferably about 0.001 to about 1 mu m, more preferably about 0.005 to about 0.5 mu m.

The dried coating film surface can be subjected to alignment treatment by irradiating ultraviolet rays having a wavelength range of, for example, from about 150 to about 450 nm. At this time, the intensity of the exposure may be, for example, an 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 photo-alignment, a liquid crystal alignment film having excellent thermal stability and high alignability can be obtained.

Liquid crystal display element

The present invention provides a liquid crystal display device including the liquid crystal alignment layer.

The liquid crystal display element can be manufactured by a conventional method known in the art. For example, one of the two substrates having the liquid crystal alignment layer according to the present invention is coated with an adhesive containing a ball spacer on the end portion of the substrate, and then the remaining one substrate is bonded together to bond the cells. The liquid crystal cell can be completed by injecting liquid crystal into the completed cell and then performing heat treatment.

The liquid crystal display element of the present invention having the liquid crystal alignment layer exhibits excellent alignment state and excellent thermal stability in the liquid crystal alignment state.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

<Examples>

Diamine  Preparation of compounds Example  One

(10) (n = 1, R1 ~ R8 = H, PG = BOC ) &Lt; / RTI &gt;

[Reaction Scheme I]

The starting material 4,4,4-trifluorobutan-1-ol (95.0 g, 0.74 mol) was dissolved in triethylamine (135 mL, 0.97 mol) and 1 L of Methylene Chloride and cooled to 0 占 폚. Methanesulfonyl chloride (63.0 mL, 62.0 mol) was slowly added thereto for 30 minutes. The mixture was stirred at 0 占 폚 for 10 minutes and reacted at room temperature for 2 hours to prepare 4,4,4-trifluorobutyl methanesulfonate (Formula 2).

The results of NMR measurement for the compound of formula (2) are as follows.

^{1 H NMR (400 MHz, CDCl} 3) δ 4.30 (t, 2H), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m, 2H)

[Reaction Scheme II]

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

The results of NMR measurement for the compound of formula (4) are as follows.

^{1 H NMR (400 MHz, CDCl} 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)

[Reaction Scheme III]

4-formylbenzoic acid (51.6 g, 0.34 mol) and 4 '- (4,4,4-trifluorobutoxy) acetophenone (84.6 g, 0.34 mol) were added to 2.2 L of 80% Thereto was added 170 ml of 25% NaOH and then reacted at room temperature for 24 hours. Then, 1.5 L of H ₂ O was added, and the mixture was cooled to 0 ° C. HCl was added until the pH became 2, and then the mixture was stirred for 2 hours to prepare a compound of formula (VI).

The results of NMR measurement for the compound of formula (6) are as follows.

¹ H NMR (400 MHz, MeOD)? 8.20 (d, 2H), 8.09 (d, IH), 8.00 (s, 4H), 7.76 (d, ), 2.45 (m, 2H), 1.99 (m, 2H)

[Reaction Scheme IV]

2,4-dinitrophenylacetic acid (70.0 g, 0.30 mol) was dissolved in 700 mL of THF, and BH ₃ SMe _{3 (} 39.0 mL, 2.00 mol) was slowly added and refluxed for 3 hours. Then, the reaction mixture was cooled to room temperature and 100 mL of 3 N HCl was added thereto to prepare 2- (2,4-dinitrophenyl) ethanol. To the autoclave was added 2- (2,4-dinitrophenyl) ethanol (64.0 g, 0.30 mol), 1.2 L of methanol and 50% wet 10% Pd / C (6.40 g, 10% w / atm atmosphere for 12 hours to prepare 2- (2,4-diaminophenyl) ethanol. 2- (2,4-diaminophenyl) ethanol (54.0 g, 0.30 mol) was dissolved in THF 600 mL / aq-NaHCO ₃ Boc ₂ O (165 g, 0.76 mol) was added slowly at 0 &lt; 0 &gt; C. Then, the reaction was carried out at room temperature for 24 hours to prepare a compound of formula (8). The compound of Formula 3 (83.6 g, 0.22 mol), EDCI (48.9 g, 0.26 mol) and DMAP (14.5 g, 0.12 mol) were dissolved in 1 L Methylene Chloride, , DIPEA (119 mL, 0.68 mol) were added and reacted at room temperature for 12 hours to prepare a compound of formula (9).

The results of NMR measurement for the compound of formula (9) are as follows.

^{1 H NMR (400 MHz, CDCl} 3) δ 8.05 (d, 4H), 7.79 (m, 2H), 7.71 (d, 2H), 7.64 (d, 1H), 7.15 (d, 1H), 7.04 (b, 2H), 2.36 (m, 2H), 2.09 (m, 2H), 3.97 (d, )

[Reaction Scheme 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, the reaction was carried out at room temperature for 4 hours and the solvent was removed by decompression to obtain the novel photoinitiator monomer (E) -2,4-diaminophenethyl 4- (3-oxo-3- (4- 4,4-trifluorobutoxy) phenyl) prop-1-enyl) benzoate (Formula 10).

The results of NMR measurement for the compound of formula (10) are as follows.

^{1 H NMR (400 MHz, CDCl} 3) δ 8.06 (m, 4H), 7.82 (d, 1H), 7.71 (d, 2H), 7.64 (d, 1H), 6.97 (d, 2H), 6.89 (d, 2H), 2.39 (s, 2H), 2.33 (m, 2H), 3.40 (m, 2H) ), 2.11 (m, 2 H)

Diamine  Preparation of compounds Example  2

(23) (n = 1, R1 ~ R8 = H, PG = BOC ) &Lt; / RTI &gt;

[Reaction Scheme VI]

The starting material 4,4,4-trifluorobutan-1-ol (95.0 g, 0.74 mol) was dissolved in triethylamine (135 mL, 0.97 mol) and Methylene Chloride (1 L) and methanesulfonyl chloride Ml, 0.81 mol) was added slowly for 30 minutes. The mixture was stirred at 0 占 폚 for 10 minutes and reacted at room temperature for 2 hours to prepare 4,4,4-trifluorobutyl methanesulfonate (Formula 2).

The results of NMR measurement for the compound of formula (2) are as follows.

^{1 H NMR (400 MHz, CDCl} 3) δ 4.30 (t, 2H), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m, 2H)

[Reaction Scheme VII]

4-hydroxyacetophenone (Formula 3) (72.5 g, 0.53 mol ) was dissolved in DMF (700 mL), a 4,4,4-trifluorobutyl methanesulfonate (Formula 2) (152 g, 0.64 mol ) prepared in Scheme VI, K ₂ Was reacted with CO ₃ (110 g, 0.80 mol) to give the compound of formula 4 (98.0 g, 75%). The compound of Formula 4 (98.0 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 below 10 ° C. The reaction was then continued for 12 hours to prepare a compound of formula 11 (120 g, 93%). Compound (12) (120 g, 0.4 mol) was added to triethylphosphite (193 mL, 1.11 mol) and refluxed for 4 hours to prepare the compound of Formula 12 (60 g, 43%).

NMR was measured for the compound of the formula (12) as follows.

^{1 H NMR (400 MHz, CDCl} 3) δ 8.01 (d, 2H), 6.93 (d, 2H), 4.12 (m, 6H), 3.61 (s, 1H), 3.53 (s, 1H), 2.34 (m, 2H), 2.08 (m, 2H), 1.33 (t, 6H)

[Reaction Scheme VIII]

(98.0 g, 87%) was prepared by adding benzophenone (Formula 13) (100 g, 0.55 mol) and KOH (30.8 g, 0.55 mol) into acetonitrile (700 mL) and refluxing for 2 hours. BuLi (2.5 M solution in hexane, 480 mL, 1.19 mol) was slowly added to a mixed solution of acetonirile (88.0 mL, 1.67 mol) and THF (900 mL) at -78 ° C under a nitrogen atmosphere and the mixture was stirred for 3 hours, 14 compound (98.0 g, 0.48 mol) and THF (600 mL) were added and reacted for 3 hours to prepare a compound of formula 15 (102 g, 87%). Concentrated sulfuric acid (460 mL) and fuming nitric acid (69.1 mL) were cooled to between 0 and -5 ° C to give the compound of Formula 15 (91.5 g, 0.37 mol) 103 g, 83%).

The compound of formula 16 (109 g, 0.32 mol) was placed in 50% H ₂ SO ₄ (2 L, v / v) and reacted at 150 ° C. and then cooled to room temperature. The reaction was then extracted to produce the compound of formula (17). The compound of Formula 17 (143 g, 0.32 mol) was dissolved in THF (1 L), BH ₃ SMe ₂ (90.5 mL, 0.96 mol) was slowly added at 0 ° C and the reaction was allowed to proceed at 50 ° C for 5 hours, Respectively.

(87.0 g, 0.25 mol), methanol (1.2 L) and 50% wet 10% Pd / C (18.0 g, 20% w / w) were placed in an autoclave. The reaction was carried out for a period of time to prepare a compound of Formula 19. The compound of formula 19 (75.0 g, 0.26 mol) was dissolved in THF (1.3 L) / sat-NaHCO ₃ (1.3 L) and Boc ₂ O (172 g, 0.79 mol) was slowly added at 0 ° C. Then, the compound of formula 20 (98.4 g, 77%) was prepared by reacting at room temperature for 24 hours.

The compound of formula 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) and DMAP (12.4 g, 0.11 mol) were added to a solution of the compound of Formula 20 (98.4 g, 0.20 mol) in acetonitrile DIPEA (87.0 mL, 0.50 mol) was added thereto, and the reaction was carried out at 10 ° C or lower to prepare a compound of Formula 21 (80.0 g, 53%).

A solution of the compound of Formula 12 (82.3 g, 0.22 mol) prepared in Scheme VII dissolved in DMF (650 mL) and a solution of 60% NaH (8.95 g, 0.23 mol) in DMF (520 mL) . A solution of the 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 (67.1 g, 65%). The compound of Formula 22 was purified using column chromatography [Hexane / EtOAc (2: 1)]. (53.1 g, 44.0 mmol) was dissolved in acetonitile (1.8 L), and a mixed solution of TMSI (15.7 mL, 110 mmol) and acetonitrile (260 mL) was added at 0 ° C. under a nitrogen atmosphere. . The solvent was removed under reduced pressure, and the product was purified using column chromatography (MC / EA = 3: 1) to prepare the compound of Formula 23 (30.0 g, 68%).

NMR was measured on the compound of formula (23) as follows.

_{^{1 H NMR (400MHz, CDCl 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,

Next, examples of producing a polyamic acid, a polyimide, a liquid crystal aligning agent, and a liquid crystal alignment film by using the diamine compound of the present invention and a carboxylic acid dianhydride and a comparative example thereof will be described. It is also described that the characteristics of an alignment film using the amine compound of the present invention are excellent by comparison and evaluation thereof.

Example  One

0.83 g of 4,4-methylene diamine (MDA), 1.17 g of p-phenylenediamine (p-PDA), 1.57 g of cholestanol (3,5-diaminobenzoate) (CDB) 1.03 g of a compound represented by Chemical Formula 10 (n = 1, R1 to R8 = H) was dissolved in 49.0 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, -Tricarboxycyclopentyl acetic anhydride (TCAAH) were added. To this, 32.7 g of g-butyrolactone (GBL) was added and reacted for 24 hours. After the 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 캜)

Example  2

0.99 g of 4,4-methylene diamine (MDA), 0.99 g of p-phenylenediamine (p-PDA), 2.09 g of cholestanol (3,5-diaminobenzoate) (CDB) 1.54 g of a compound represented by Chemical Formula 10 (n = 1, R1 to R8 = H) was dissolved in 53.2 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, -Tricarboxycyclopentyl acetic anhydride (TCAAH) were added. 35.5 g of g-butyrolactone (GBL) was added thereto and reacted for 24 hours. After the reaction, 39.4 g of g-butyrolactone (GBL), 2.96 g of N-methyl-2-pyrrolidone (NMP) and 56.2 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent B. (Viscosity 10 cP, 25 캜)

Example  3

0.63 g of 4,4-methylene diamine (MDA), 0.84 g of p-phenylenediamine (p-PDA), 2.61 g of cholestanol (3,5-diaminobenzoate) (CDB) 2.05 g of a compound of the formula 10 (n = 1, R 1 to R 8 = H) in 1 was dissolved in 57.3 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, -Tricarboxycyclopentyl acetic anhydride (TCAAH) were added. To this, 38.2 g of g-butyrolactone (GBL) was added and reacted for 24 hours. After the reaction, 42.4 g of g-butyrolactone (GBL), 3.19 g of N-methyl-2-pyrrolidone (NMP) and 60.5 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent C. (Viscosity 7 cP, 25 캜)

Example  4

0.83 g of 4,4-methylene diamine (MDA), 1.17 g of p-phenylenediamine (p-PDA), 1.57 g of cholestanol (3,5-diaminobenzoate) (CDB) 2.01 g of the compound of the formula 23 (n = 1, R1 to R8 = H) in 2 was dissolved in 54.3 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, -Tricarboxycyclopentyl acetic anhydride (TCAAH) were added. To this, 32.2 g of g-butyrolactone (GBL) was added and reacted for 24 hours. After the 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 a 5 wt% liquid crystal aligning agent D. (Viscosity 10 cP, 25 캜)

Example  5

0.99 g of 4,4-methylene diamine (MDA), 0.99 g of p-phenylenediamine (p-PDA), 2.09 g of cholestanol (3,5-diaminobenzoate) (CDB) 2-pyrrolidone (NMP) was dissolved in 61.2 g of N-methyl-2-pyrrolidone (NMP) under nitrogen atmosphere, -Tricarboxycyclopentyl acetic anhydride (TCAAH) were added. To this, 40.8 g of g-butyrolactone (GBL) was added and reacted for 24 hours. After the reaction, 5 wt% of liquid crystal aligning agent E was obtained by adding 45.3 g of g-butyrolactone (GBL), 3.40 g of N-methyl-2-pyrrolidone (NMP) and 64.6 g of butyl cellosolve (BC) (Viscosity 9 cP, 25 캜)

Example  6

0.50 g of 4,4-methylene diamine (MDA), 0.68 g of p-phenylenediamine (p-PDA), 2.10 g of cholestanol (3,5-diaminobenzoate) 3.23 g of the compound of Formula 23 (n = 1, R 1 to R 8 = H) in 2 was dissolved in 54.6 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, 3.60 g of tricarboxycyclopentyl acetic anhydride (TCAAH) was added. To this, 36.4 g of g-butyrolactone (GBL) was added and reacted for 24 hours. After the reaction, 40.4 g of g-butyrolactone (GBL), 3.03 g of N-methyl-2-pyrrolidone (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 캜)

Comparative Example 1

, 0.75 g of 4,4-methylene diamine (MDA), 1.02 g of p-phenylenediamine (p-PDA) and 5.56 g of cholestanol (3,5-diaminobenzoate) (CDB) -2-pyrrolidone (NMP), and then 5.40 g of 2,3,5-tricarboxycyclopentylacetic anhydride (TCAAH) was added while maintaining the temperature at 20 ° C. To this, 46.0 g of g-butyrolactone (GBL) was added and reacted for 24 hours. After the reaction, 97.15 g of g-butyrolactone (GBL), 72.9 g of N-methyl-2-pyrrolidone (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 캜)

Liquid crystal alignment film and The liquid crystal cell  Produce

The liquid crystal aligning agents A to G obtained by the above method were filtered using a filter having a pore diameter of 1 mu m. The liquid crystal aligning agents A to G were formed on a transparent conductive film including an ITO film provided on one side of a glass substrate in two steps of a spinning speed of 500 rpm, a rotation time of 10 seconds, a rotation number of 1800 rpm, and a rotation time of 20 seconds The coating film was formed by pre-curing at 180 ° C for 60 seconds and main curing at 210 ° C for 20 minutes to remove the solvent.

Subsequently, the substrate was exposed to light at an intensity of 300 mJ / cm ² and an intensity of 10 mW using an exposure machine to prepare two substrates (one pair) having a liquid crystal alignment film. Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 4 占 퐉 was applied to the outer edge portions of the substrate having the liquid crystal alignment film of the pair of liquid crystal alignment films, and then the liquid crystal alignment film surfaces were superimposed on each other so as to face each other, And cured. Next, a nematic liquid crystal (n _e 1.5601, n _o 1.4780) was filled between the substrates from the liquid crystal injection port, and then the liquid crystal injection hole was sealed with an acrylic light curing adhesive to produce a liquid crystal display device.

<Experimental Example>

The liquid crystal cell  Property evaluation

Assessment Methods

1. Viscosity

The kinematic viscosity was measured using a cannon viscometer at 25 ° C, the specific gravity was measured with a specific gravity meter, and the viscosity was calculated by multiplying the specific gravity by two values.

2. The angle of pre-

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

3. Liquid crystal orientation

The presence or absence of an abnormal domain in the liquid crystal display element when a voltage was turned on or off in the liquid crystal display element was observed under a microscope, and it was judged that the abnormal domain was not present.

4. Voltage maintenance rate

A voltage of 5 V was applied to the liquid crystal display element for 60 microseconds, and the voltage maintenance ratio after 16.67 milliseconds from the application of the voltage was measured.

The evaluation results of physical properties of the liquid crystal display device manufactured by the 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 alignment properties of Examples 1 to 6 are remarkably superior to those of Comparative Examples.

Comparison of characteristics of liquid crystal cell division Square Voltage holding ratio Orientation Before exposure After exposure Example 1 89 ° 99% Bad Good Example 2 89 ° 99% Bad Good Example 3 89 ° 99% Bad Good Example 4 89 ° 99% Bad Good Example 5 89 ° 99% Bad Good Example 6 89 ° 99% Bad Good Comparative Example 1 89 ° 99% Bad Bad

Examples and comparative examples of the present invention are shown in Table 2 below.

Referring to the following Table 2, it can be seen that the domains after the exposure in Examples 1 to 6 are invisible although the domains are not visible, but the difference between the domains before and after exposure is poor in the comparative example.

Liquid crystal orientation picture division Orientation Before exposure After exposure Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Comparative Example 1

Claims (11)

A diamine compound represented by the following formula (10):
[Chemical formula 10]

In Formula 10,
n is an integer from 1 to 5;
R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms.
delete A diamine compound represented by the following formula (23):
(23)

In the formula (23)
n is an integer from 1 to 5;
R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms.
delete A liquid crystal aligning agent comprising a polyamic acid or polyimide obtained by reacting a diamine component containing a diamine compound represented by the following formula (10) with a tetracarboxylic dianhydride:
[Chemical formula 10]

In Formula 10,
n is an integer from 1 to 5;
R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms.
A liquid crystal aligning agent comprising a polyamic acid or a polyimide obtained by reacting a diamine component containing a diamine compound represented by the following formula (23) with a tetracarboxylic dianhydride:
(23)

In the formula (23)
n is an integer from 1 to 5;
R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms.
The method of claim 5 or 6, wherein the diamine component is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- 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'- , 3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzo (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( Bis (4-aminophenoxy) phenyl] sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 4-bis (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 Diamine, octamethylene diamine, nonamethylene diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydro dicyclopentadienyl alkenylene diamine, tricyclo [6.2.1.0 ^2,7] - undecylenic dimethyl-diamine, 4 , 4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and other aliphatic or alicyclic diamines; 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, (3,5-diaminophenyl) -3-decylsuccinimide and 1- (3,5-diaminophenyl) - 3- Wherein the liquid crystal aligning agent further comprises at least one diamine compound selected from the group consisting of octadecylsuccinimide and octadecylsuccinimide.
A liquid crystal alignment film formed from the liquid crystal aligning agent of any one of claims 5 and 6.
10. A liquid crystal display element comprising the liquid crystal alignment film of claim 8.
Reacting a compound represented by the following formula (6) with a compound represented by the following formula (8) to prepare a compound represented by the following formula (9); And
A process for producing a diamine compound represented by the following formula (10), which comprises the step of removing the protecting group PG of the compound represented by the following formula (9)
[Chemical Formula 6]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas (6), (8), (9)
n is an integer from 1 to 5;
R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms;
PG is BOC (tert-butyloxycarbonyl).
Reacting a compound represented by the following formula (12) with a compound represented by the following formula (21) to prepare a compound represented by the following formula (22); And
A process for producing a diamine compound represented by the following formula (23), which comprises a step of removing the protecting group PG of the compound represented by the following formula (22).
[Chemical Formula 12]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

In the above formulas (12), (21), (22) and (23)
n is an integer from 1 to 5;
R 1 to R 8 are the same or different and each independently H or an alkyl group having 1 to 10 carbon atoms;
PG is BOC (tert-butyloxycarbonyl).