KR20130001144A - Photoactive crosslinking compound, method for preparing the same, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

This invention relates to a photoactive crosslinking agent compound, its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element. More specifically, it relates to a photoactive crosslinking agent compound having a novel structure, a manufacturing method thereof, a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element.
According to the present invention, it is possible to provide a liquid crystal aligning agent having high vertical alignment performance, good storage stability, excellent transparency, and excellent liquid crystal alignment, printability and electrical properties. Moreover, the stability and film | membrane intensity | strength of the pretilt angle of a liquid crystal aligning film can be improved more, and the pretilt of a liquid crystal can be formed only by UV exposure.

Description

Photoactive crosslinking compound, Method for preparing the same, Liquid crystal alignment agent, Liquid crystal alignment film, and Liquid crystal display device

This invention relates to a photoactive crosslinking agent compound, its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element. More specifically, it relates to a photoactive crosslinking agent compound having a novel structure, a manufacturing method thereof, a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element.

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 plays a role of a switch of polarized 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 layer include an inorganic gradient deposition method, Langmuir-Blodgett (LB) method, polymer stretching method, rubbing method, etc., and new alignment methods include photo-alignment method and ion beam irradiation method. It is proposed. Among them, the most commonly used method is a rubbing method of rubbing a substrate surface 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 alignment treatment, 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 manufacturing process of the alignment layer including the separated alignment pixels becomes complicated. Finally, special equipment is required to uniformly rub a large substrate.

As a technique for overcoming these disadvantages, a photo-alignment technique for preparing a liquid crystal alignment layer by irradiating polarized ultraviolet (UV) light onto the polymer film without rubbing treatments has emerged. Photo-alignment technology utilizes 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, light having a linear polarization directional light is used, and a photoreaction process of a polymer film such as photoisomerization, photopolymerization or photolysis is required, and polarization of light irradiated with the direction of liquid crystal molecules Various conditions are required, such as being able to be controlled by direction.

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. For this purpose, 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 electrodes or forming protrusions on 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 in electro-optic characteristics such as response speed and initial light leakage occur.

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

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 is an object to provide a novel photoactive crosslinking agent compound for producing a liquid crystal aligning agent.

Moreover, an object of this invention is to provide the manufacturing method of the said photoactive crosslinking agent compound.

In addition, the present invention is a photoactive crosslinker compound; And it aims at providing the liquid crystal aligning agent containing polyamic acid or polyimide.

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.

In order to achieve the above object, the present invention provides a photoactive crosslinking compound represented by the following formula (I).

(I)

In Formula I,

이고 나머지는 H 이고;At least one of X ₁ , X ₂ , X _3, and X ₄

And the rest is H;

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;

또는

이고;A is

or

ego;

또는

이며;B is

or

;

n is an integer of 1 to 20;

The present invention also provides a photoactive crosslinking agent compound represented by the following general formula (II).

≪ RTI ID = 0.0 &

In Chemical Formula II,

이고 나머지는 H 이고;At least one of X ₁ , X ₂ , X _3, and X ₄

And the rest is H;

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;

또는

이고;A is

or

ego;

또는

이며;B is

or

;

n is an integer of 1 to 20;

The present invention also provides a photoactive crosslinker compound; And a polyamic acid or a polyimide.

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 another aspect, the present invention provides a method for producing a photoactive crosslinking compound represented by the formula (20) comprising the step of reacting a compound represented by the formula (19), and a compound represented by the formula (5).

[Formula 19]

[Chemical Formula 5]

[Chemical Formula 20]

In Chemical Formulas 5, 19, and 20,

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;

n is an integer from 1 to 20.

In another aspect, the present invention provides a method for producing a photoactive crosslinking agent compound represented by the formula (40) comprising the step of reacting a compound represented by the formula (39), and a compound represented by the formula (28).

[Chemical Formula 39]

(28)

[Formula 40]

In Chemical Formulas 28, 39, and 40,

R ₁ To R ₄ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;

n is an integer of 1 to 20;

According to the present invention, by using the optical alignment technology that is a method for aligning the liquid crystal molecules without rubbing, it is possible to ensure the safety and economical efficiency of the process progress, and to establish an environmentally friendly manufacturing process.

Moreover, according to the liquid crystal aligning agent containing the photoactive crosslinking agent compound of this invention, the stability and film | membrane intensity | strength of the pretilt angle of a liquid crystal aligning film can be improved more, the pretilt of a liquid crystal is formed only by UV exposure, and the process progress is simplified. This can reduce production costs and improve product productivity.

In addition, it is possible to provide a liquid crystal aligning agent having high vertical alignment performance, good storage stability, excellent transparency, and excellent liquid crystal alignment property, printability and electrical properties.

1 shows a liquid crystal alignment photograph of the liquid crystal display device manufactured by Example 3 of the present invention.
2 shows a liquid crystal alignment photograph of the liquid crystal display device manufactured by Comparative Example 1. FIG.

The liquid crystal aligning agent prepared from the photoactive crosslinking agent compound of the present invention can produce a liquid crystal aligning film using a photoalignment technique of irradiating polarized ultraviolet (UV) light onto a polymer film without rubbing treatment.

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, light having a linear polarization directional light is used, and a photoreaction process of a polymer film such as photoisomerization, photopolymerization or photolysis is required, and polarization of light irradiated with the direction of liquid crystal molecules Various conditions are required, such as being able to be controlled by direction.

The photoisomerization reaction has the disadvantage of adverse effects such as adverse reactions, contamination of the liquid crystal layer by decomposition products in the photolysis reaction, and the initial poly (vinyl cinnamate) polymers have been studied in the photopolymerization reaction. Because of the short wavelength of the ultraviolet rays, there is a problem in mass production such as the general purpose large exposure apparatus being difficult to use.

In general, polyimide resins that have been widely used as photo-alignment agents refer to high heat-resistant resins prepared by condensation polymerization of aromatic tetracarboxylic acids or derivatives thereof with aromatic diamines or aromatic diisocyanates, 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) as the aromatic diamine component. -PDA), 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 2,2'-bisaminophenylhexafuluropropane (HFDA), metabisaminophenoxydi Phenylsulfone (m-BAPS), parabisaminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R) , 2,2'-bisaminophenoxyphenylpropane (BAPP), 2,2'-bisaminophenoxyphenylhexafluoropropane (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. For this purpose, 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 electrodes or forming protrusions on 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 in electro-optic characteristics such as response speed and initial light leakage occur.

The present invention provides a photoactive cross-linking compound compound and a liquid crystal aligning agent comprising the same, by forming the alignment liquid crystal molecules in the liquid crystal display device by using such a photo-alignment technology, which can form pretilt only by UV exposure after forming the alignment layer. I would like to.

Certain terms used herein are used for the purpose of describing the present invention in detail to those skilled in the art, but are not used to limit the scope of the present invention as defined in the claims or the claims.

Hereinafter, the present invention will be described in more detail with reference to Examples, a photoactive crosslinking agent compound, a method for producing the same, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display device.

However, embodiments according to the present invention can be modified in many different 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.

Photoactive Cross-linking agent  Compound and preparation method thereof

According to one aspect of the present invention, the photoactive crosslinker compound of the present invention may be represented by the following formula (I).

(I)

In Formula I,

이고 나머지는 H 이고;At least one of X ₁ , X ₂ , X _3, and X ₄

And the rest is H;

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;

또는

이고;A is

or

ego;

또는

이며;B is

or

;

n is an integer of 1 to 20;

According to an embodiment of the present invention, in formula (I), R ₁ To R ₈ is H and n may be an integer from 1 to 5.

According to one embodiment of the present invention, for example, the compound of Formula I may be a compound represented by the following Formula 20, Formula 22 or Formula 24.

[Chemical Formula 20]

[Formula 22]

≪ EMI ID =

In the above formula (20)

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group; n is an integer from 1 to 20.

According to another aspect of the invention, there is provided a method for producing a photoactive crosslinking compound represented by the formula (20).

The method for preparing a photoactive crosslinking agent compound represented by Formula 20 includes reacting a compound represented by Formula 19 with a compound represented by Formula 5 below.

[Formula 19]

[Chemical Formula 5]

[Chemical Formula 20]

In Chemical Formulas 5, 19 and 20,

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group; n is an integer from 1 to 20.

More specifically, the method for preparing a photoactive crosslinking compound represented by Formula 20 may be prepared by performing the following Schemes 1, 2, 3, 4, and 5 step by step, but the present invention is not limited thereto.

[Reaction Scheme 1]

Scheme 2

Scheme 3

[Reaction Scheme 4]

Scheme 5

In Schemes 1 to 5, R ₁ To R ₈ and n are as defined in formula (I) above.

Starting compounds, intermediate compounds and product compounds used in Schemes 1 to 5 may be represented by the formula 1 to 24.

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Formula 22]

(23)

≪ EMI ID =

In Chemical Formulas 1 to 24, R ₁ To R ₈ and n are as defined in formula (I) above.

In addition, the compounds of Formula 22 and Formula 24 may be prepared in a manner similar to those of Schemes 1 to 5 using the compounds of Formulas 21 and 23 instead of the compounds of Formula 6 in Schemes 1 to 5, respectively.

According to another aspect of the present invention, the photoactive crosslinker compound of the present invention may be represented by the following formula (II).

≪ RTI ID = 0.0 &

In Chemical Formula II,

이고 나머지는 H 이고;At least one of X ₁ , X ₂ , X _3, and X ₄

And the rest is H;

R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;

또는

이고;A is

or

ego;

또는

이며;B is

or

;

n is an integer of 1 to 20;

According to an embodiment of the present invention, in Formula II, R ₁ To R ₈ is H and n may be an integer from 1 to 5.

According to an embodiment of the present invention, for example, Formula II may be represented by the following Formula 40.

[Formula 40]

In Chemical Formula 40,

R ₁ To R ₄ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group; n is an integer from 1 to 20.

According to another aspect of the present invention, a method of preparing a photoactive crosslinking compound represented by Formula 40 is provided.

The method for preparing a photoactive crosslinking agent compound represented by Formula 40 includes reacting a compound represented by Formula 39 with a compound represented by Formula 28.

[Chemical Formula 39]

(28)

[Formula 40]

In Chemical Formulas 28, 39, and 40,

R ₁ To R ₄ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group; n is an integer from 1 to 20.

More specifically, the method for preparing the photoactive crosslinking compound represented by Formula 40 may be prepared by the following Schemes 6 and 7, but the present invention is not limited thereto.

[Reaction Scheme 6]

[Reaction Scheme 7]

In Schemes 6 and 7, wherein R ₁ To R ₄ and n are as defined in Formula II above.

Starting compounds, intermediate compounds and product compounds used in Schemes 6 and 7 may be represented by the following formula (25 to 40).

(25)

(26)

(27)

(28)

[Formula 29]

(30)

(31)

(32)

(33)

[Formula 34]

(35)

(36)

[Formula 37]

(38)

[Chemical Formula 39]

[Formula 40]

In Formulas 25 to 40, R ₁ To R ₄ and n are as defined in formula (II).

The novel photoactive crosslinking compound of the present invention as described above further improves the stability and film strength of the pretilt angle of the liquid crystal alignment film. Specifically, when the liquid crystal aligning agent is prepared by adding the photoactive crosslinking compound of the present invention to polyamic acid or polyimide, the stability and film strength of the pretilt angle of the liquid crystal aligning film can be further improved.

Liquid crystal Alignment agent

According to another aspect of the present invention, the present invention is a photoactive crosslinker compound described above; And a polyamic acid or a polyimide.

The said polyamic acid can be obtained by making a diamine compound and tetracarboxylic dianhydride react, and the said polyimide can be obtained by imidating by dehydrating and ring-closing a polyamic acid.

According to one embodiment of the present invention, the liquid crystal aligning agent may include 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight of the photoactive crosslinking compound, based on 100 parts by weight of the polyamic acid or polyimide.

In the present invention, as the diamine compound which can be used to obtain a polyamic acid, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-dia Minodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- Diaminobenzanilide, 4,4'-diaminodiphenylether, 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'-diaminodiphenylether, 3, 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) Phenyl] sulfone, 1,4-bis (4-amino Phenoxy) 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) 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'-dia Minobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- ( 4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [ (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, di (4-aminophenyl) benzidine, 1- (4-aminophenyl) -1,3,3-trimethyl-1H-indene -5-amine, 1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentame Diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydro dicyclopentadienyl alkenylene diamine, tricyclo [6.2.1.0 ^2,7 Aliphatic or alicyclic diamines such as] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane; And 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-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5 -Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine , 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl) -3 And at least one diamine compound selected from the group consisting of two primary amino groups in the molecule such as octadecyl succinimide and diamine further containing a nitrogen atom in addition to the primary amino group.

Examples of the tetracarboxylic dianhydride used to synthesize polyamic acid or polyimide in the liquid crystal aligning agent of the present invention include alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. Can be mentioned.

Specific examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutanetetracar Acid dianhydride, 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-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene -1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3- Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-di Aqueous, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [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 -7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 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) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1 ] Octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione) etc. are mentioned.

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 dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4, 4'-tetraphenyl silanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic 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'-perfluoroisopropylidenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydrides, bis (phthalic acid) phenylphosphineoxide dianhydrides, p-phenylene-bis (triphenylphthalic acid) dianhydrides, m-phenylene-bis (triphenylphthalic acid) dianhydrides, bis (triphenylphthalic acid) -4 , 4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydro trimellitate ), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2 And 2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimelitate).

A polyamic acid can be obtained by making the said diamine compound and the said tetracarboxylic dianhydride react.

The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the synthesis reaction of the polyamic acid is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine compound. More preferably, it is a ratio which becomes 0.7 to 1.2 equivalent.

The synthesis reaction of the polyamic acid may be carried out in an organic solvent for 1 to 72 hours, preferably 3 to 48 hours, under temperature conditions of -20 to 150 ° C, preferably 0 to 100 ° C.

In this case, the organic solvent is not particularly limited as long as it can dissolve the polyamic acid produced. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide , Amide compounds such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, dimethyl sulfoxide, γ Aprotic compounds such as butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenolic compounds, such as m-cresol, xylenol, a phenol, and a halogenated phenol, etc. can be illustrated.

In addition, the said organic solvent can use together alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, a hydrocarbon etc. which are poor solvents of a polyamic acid in the range which does not precipitate the produced polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, lactic acid Butyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 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, o- Dichlorbenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, etc. are mentioned. As described above, a reaction solution obtained by dissolving a polyamic acid can be obtained. Then, 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. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then 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 polyamic acid obtained as mentioned above.

The dehydration ring closure of the polyamic acid is preferably heated by (i) a method of heating the polyamic acid, or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution, if necessary. It is done by the method. The reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, Preferably it is 60-170 degreeC. The reaction time is 1 to 8 hours, preferably 3 to 5 hours. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall.

On the other hand, as a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, and a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said (ii) polyamic acid. Although the usage-amount of a dehydrating agent changes with the imidation ratio made into the objective, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic-acid structure of a polyamic acid.

As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine 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 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be made higher, so that the usage-amount of said dehydrating agent and dehydrating ring closure agent is large. As an organic solvent used for dehydration ring-closure 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 0 to 180 ° C, preferably 10 to 150 ° C. The reaction time is 1 to 8 hours, preferably 3 to 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 may be used for manufacture of a liquid crystal aligning agent after refine | purifying the obtained polyimide.

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 for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, and for the production of the liquid crystal aligning agent after isolating polyimide. It may be used, 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 a 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 is a polyimide which dehydrated the polyamic acid or polyamic acid obtained by reaction of the tetracarboxylic dianhydride and a diamine compound as mentioned above, the photoactive crosslinking agent compound, and the other suitably mix | blended as needed. An additive is included, and the components may preferably be dissolved in an organic solvent.

As said organic solvent which can be used for the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-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-n-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 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.

Solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably it is 1 To 10% by weight. 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.

According to one embodiment of the present invention, a liquid crystal aligning agent may be prepared by adding the photoactive crosslinking compound according to the present invention to the polyamic acid.

According to another embodiment of the present invention, the photoactive crosslinking agent compound may be added to a polyimide obtained from a polyamic acid to prepare a liquid crystal aligning agent.

When the liquid crystal aligning agent including the photoactive crosslinking agent compound is irradiated with UV, an effective vertical alignment with respect to the liquid crystal alignment layer may be induced by forming a crosslinked structure by a photoreactor included in the structure of the photoactive crosslinking agent compound.

The photoactive crosslinking agent compound can further improve the stability and film strength of the pretilt angle of the liquid crystal alignment film to be formed, and can perform photo alignment without a rubbing treatment by UV exposure.

According to one embodiment of the present invention, the liquid crystal aligning agent may include 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight of the photoactive crosslinking compound, based on 100 parts by weight of the polyamic acid or polyimide. If the amount of the photoactive crosslinking agent compound is less than 0.1 part by weight, it is difficult to expect a vertical alignment improvement effect. If the photoactive crosslinker compound is contained in an excess of 40 parts by weight, the basic physical properties of the liquid crystal aligning agent may be lowered.

Liquid crystal alignment film and liquid crystal display element

A liquid crystal aligning film can be formed by apply | coating and heating the liquid crystal aligning agent of this invention on a base material.

The said liquid crystal aligning agent can be apply | coated by methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, for example, and then forms a liquid crystal aligning film by heating the apply | coated surface.

After application of the liquid crystal aligning agent, preliminary heating (pre-baking) can be preferably performed for the purpose of preventing liquid flow of the applied alignment agent. The preliminary baking 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 baking (post-baking) temperature becomes like this. Preferably it is about 80 to about 300 degreeC, More preferably, it is about 120 to about 250 degreeC. Thus, 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 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 aligning film formed, Preferably it is about 0.001 to about 1 micrometer, More preferably, it may be about 0.005 to about 0.5 micrometer.

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 photo-alignment, a liquid crystal aligning film having excellent thermal stability and high alignment ability can be obtained.

In addition, a liquid crystal display device having the liquid crystal alignment layer may be manufactured by a conventional method known in the art. For example, after the resin adhesive is applied to the outer edge of the substrate having a pair of liquid crystal alignment film, the surface of the liquid crystal alignment film is overlapped and pressed to face each other, the adhesive is cured and the liquid crystal is filled between the substrates from the liquid crystal inlet, and then the liquid crystal is applied. A liquid crystal display device can be manufactured by the method of sealing an injection hole.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

< Example >

Photoactive Cross-linking agent  Preparation of compounds

Example  1: Formula 20 (n = 1, R1 ~ R8 Photoactivity of = H) Cross-linking agent  Preparation of compounds

[Reaction Scheme 1]

Starting material 4,4,4-trifluorobutan-1-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 ° C. for 10 minutes and reacted at room temperature for 2 hours to prepare 4,4,4-trifluorobutyl methanesulfonate (Formula 2).

Scheme 2

methyl-4-hydroxybenzoate (Formula 3) (87.3 g, 0.57 mol), K ₂ CO ₃ (95.2 g, 0.69 mol), 4,4,4-trifluorobutyl methanesulfonate (Formula 2) (130.3 g, 0.63 mol) It was put in L acetonitrile and refluxed for 12 hours. The reaction was cooled to room temperature and extracted to give a compound of formula 4. The compound of Formula 4 (160 g, 0.57 mol) was added to 1.5 L methanol, and 370 mL of 25% NaOH was added thereto and reacted for 4 hours to prepare a compound of Formula 5.

Scheme 3

Into the autoclave add 4-nitrocinnamic acid (Formula 6) (110 g, 0.57 mol), methanol 1.5 L, 50% wet 10% Pd / C (11.0 g, 10% w / w.) And hydrogen (3 atm) The compound of formula 7 was prepared by reacting for 24 hours in an atmosphere.

Compound 7 (95.0 g, 0.57 mol) is dissolved in 1,4-dioxane (1 L) / Na ₂ CO ₃ (120.6 g in H ₂ O 1.2 L), and Boc ₂ O (149 g, 0.68 mol) is 0 ° C. After the addition, the reaction was carried out at room temperature for 3 hours to prepare a compound of formula 8 (145 g, 96%).

The compound of Formula 8 (61.0 g, 0.23 mol) and TEA (38.6 mL, 0.27 mol) were added to 700 mL of DME, and ethyl chloroformate (26.3 mL, 0.27 mol) was added at 0 ° C. and reacted for 24 hours. The reaction is cooled to 0 ° C. and NaBH ₄ (14.8 g, 0.39 mol) is added. The mixture was reacted for 12 hours to obtain a compound of formula 9.

Compound (125 g), PCC (196 g, 0.91 mol), and silica gel (100 g) of Chemical Formula 9 were added to Methylene Chloride (1.7 L), and reacted at room temperature for 3 hours to prepare Compound 10 (57.8 g). It was.

[Reaction Scheme 4]

4-hydroxyacetophenone (Formula 11) (100 g, 0.73 mol) was dissolved in EtOAc (1.5 L) and CuBr ₂ (328 g, 1.47 mol) was added at room temperature. Compound 12 was prepared by refluxing for 12 hours, and compound 12 of formula (116 g, 0.54 mol) and 3,4-dihydro-2H-pyran (200 mL, 2.16 mol) contained PPTS (4.10 g, 0.016 mol). Methylene Chloride was added to 1.5 L, and reacted at room temperature for 4 hours to prepare a compound of Formula 13.

Compound 13 of formula 13 (175 g, 0.54 mol) and PPh ₃ (145 g, 0.55 mol) were added to acetonitrile (1.5 L) and reacted for 6 hours at room temperature to prepare compound of formula 14. After dissolving the compound of Formula 14 (290 g, 0.52 mol) in THF (2.5 L), 2 M Na ₂ CO ₃ (2 L) was added and reacted for 12 hours to give the compound of Formula 15 (226 g, 91%). Prepared.

Scheme 5

Compound 10 (73.8 g, 0.29 mol) and compound 15 (171 g, 0.36 mol) prepared in Scheme 4 were dissolved in toluene, and refluxed for 7 hours to prepare compound 16 (102 g, 76%). .

Compound 16 (102 g, 0.22 mol) was dissolved in 2.0 L Methylene Chloride and TFA (200 mL) was added at 0 ° C. for 1 hour. And reacted for 4 hours at room temperature to give a compound of formula 17 (70.2 g, 91%).

A compound of formula 17 (70.2 g, 0.20 mol) was dissolved in 200 mL of AcOH, and epichlorohydrin (20.3 g, 0.22 mol) was added thereto to react for 12 hours to prepare a compound of formula 18 (85.0 g, 92%). Compound 18 (85.0 g, 0.18 mol) and PPTS (5.67 g, 0.02 mol) were added to methanol and reacted for 4 hours to prepare a compound of formula 19 (60.0 g, 88%).

A compound of formula 19 (60.0 g, 0.16 mol) was dissolved in 1 L of Methylene Chloride, the compound of formula 5 prepared in Scheme 2 (51.0 g, 0.20 mol), EDCI (45.9 g, 0.25 mol), DMAP (10.4 g) , 0.09 mol) and DIPEA (89.0 mL, 0.51 mol) were added below 10 ° C. After reacting this for 12 hours at room temperature, the product was extracted to obtain a product. The product was purified using column chromatography [MC / EtOAc (20: 1)] to prepare a compound of formula 20 (91.4 g, 94%). .

Example  2: formula 40 (n = 1, R1 ~ R4 Photoactivity of = H) Cross-linking agent  Preparation of compounds

[Reaction Scheme 6]

4-hydroxyacetophenone (Formula 25) (72.5 g, 0.53 mol) is dissolved in DMF (700 mL), and 4,4,4-trifluorobutyl methanesulfonate prepared in Scheme 1 of Example 1 (Formula 2) (152 g, 0.64 mol), and reacted with K ₂ CO ₃ (110 g, 0.80 mol) to give formula 26 compound (98.0 g, 75%).

Compound 26 (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 10 ° C or below. After reacting for 12 hours to obtain a compound of formula 27 (120 g, 93%).

Compound 27 (120 g, 0.4 mol) was added to triethylphosphite (193 mL, 1.11 mol) and refluxed for 4 hours to prepare a compound of formula 28 (60 g, 43%).

[Reaction Scheme 7]

Benzophenone (Formula 29) (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 prepare a compound of Formula 30 (98.0 g, 87%). 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) in a nitrogen atmosphere at -78 ° C, and stirred for 3 hours. 30 compound (98.0 g, 0.48 mol) and THF (600 mL) were added thereto, and reacted for 3 hours to prepare a compound of formula 31 (102 g, 87%).

Concentrated sulfuric acid (460 mL) and fuming nitric acid (69.1 mL) were cooled from 0 to -5 ° C, and then the compound of Formula 31 (91.5 g, 0.37 mol) was added and reacted at 10 ° C or less for 5 hours to react with the compound of Formula 32 ( 103 g, 83%) was prepared. Compound 32 (109 g, 0.32 mol) was placed in 50% H ₂ SO ₄ (2 L, v / v), reacted at 150 ° C., and then cooled to room temperature. After the reaction was extracted to prepare a compound of formula 33.

Compound 33 (143 g, 0.32 mol) was dissolved in EtOH (1 L), HCl was added, and then refluxed for 12 hours to prepare compound 34 (129 g, 94%). In an autoclave, a compound of formula 34 (129 g, 0.30 mol), methanol (1.5 L), 10% Pd / C (20 g, 20% w / w) was added and reacted for 24 hours in a hydrogen (3 atm) atmosphere. 35 compound was prepared.

Compound 35 (113 g, 0.30 mol) was dissolved in 300 mL of AcOH, and epichlorohydrine (33.3 g, 0.36 mol) was added thereto, and reacted for 12 hours to prepare compound 36 (148 g, 83%). Compound 36 (148.6 g, 0.25 mol) was dissolved in EtOH (1 L), NaOH (20 g, 0.50 mol) was dissolved in water, and then refluxed for 3 hours to prepare compound 37 (107.7 g, 80%). It was.

Compound 37 (107.7 g. 0.20 mol) was dissolved in THF (1 L), BH ₃ SMe ₂ (45.5 g, 0.60 mol) was slowly added at 0 ° C, and reacted at 50 ° C for 5 hours to prepare compound 38. It was. In a solution of compound 38 (91.9 g, 0.18 mol) in acetonitrile (1.5 L), 4-formylbenzoic acid (80.6 g, 0.54 mol), EDCI (148.4 g, 0.72 mol), DMAP (12.4 g, 0.11 mol), DIPEA (78.3 mL, 0.45 mol) was added thereto and reacted at 10 ° C. or less to prepare a compound of Formula 39 (77.4 g, 55%).

The compound of formula 28 prepared in Scheme 6 (93.5 g, 0.25 mol) was dissolved in DMF (600 mL), and a solution containing 60% NaOH (9.72 g, 0.25 mol) dispersed in DMF (400 mL) was added thereto. Reacted. A compound of Formula 39 (77.4 g, 0.10 mol) dissolved in DMF (600 mL) was mixed and reacted at room temperature for 14 hours, followed by purification using column chromatography [hexane / EtOAc (2: 1)]. Compound 40 was prepared (86.1 g. 70%).

Preparation of liquid crystal aligning agent

Example  3

0.75 g of 4,4-methylene diamine (MDA), 1.02 g of p-phenylene diamine (p-PDA), and 5.62 g of cholestanol (3,5-diamino benzoate) (CDB) were added under N-methyl atmosphere. It was dissolved in 69.0 g of 2-pyrrolidone (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, 51.13 g of g-butyrolactone (GBL), 3.83 g of N-methyl-2-pyrrolidone (NMP), and 72.9 g of butyl cellosolve (BC) were added to obtain a 5 wt% polyamic acid solution. (Viscosity 12 cP, 25 ° C)

The liquid crystal aligning agent was manufactured by adding the photoactive crosslinking agent compound of Example 1 to 5 wt% here.

Comparative example  One

A liquid crystal aligning agent was prepared in the same manner as in Example 3 except that the photoactive crosslinking compound was not added.

Manufacture of liquid crystal aligning film and liquid crystal display element

The liquid crystal aligning agents obtained in Example 3 and Comparative Example 1 above were each filtered using a filter having a pore size of 1 μm. This liquid crystal aligning agent was applied on a transparent conductive film including an ITO film provided on one surface of a glass substrate using a spinner in two stages under the conditions of rotational speed 500 rpm, rotation time 10 seconds, rotation speed 1800 rpm and rotation time 20 seconds, 60 seconds precure at 180 ℃, the main cure for 20 minutes at 210 ℃ to remove the solvent, thereby forming a coating film.

Thereafter, the substrate was exposed to light for 30 seconds at an intensity of 300 mJ / cm ² and 10 mW using an exposure machine to prepare two substrates (pair) having a liquid crystal alignment film. Subsequently, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter of 4 micrometers to each outer edge part which has a liquid crystal aligning film of the board | substrate which has this pair of liquid crystal aligning film, it overlaps and compresses so that a liquid crystal aligning film surface may face, and an adhesive agent is Cured. Subsequently, a nematic liquid crystal (n _e 1.5601, n _o 1.4780) was charged between the liquid crystal inlet and the substrate, and then the liquid crystal inlet was sealed with an acrylic photocuring adhesive to manufacture a liquid crystal display device.

< Experimental Example >

Physical property evaluation of liquid crystal display device

Assessment Methods

1. Viscosity

Kinematic viscosity was measured using a cannon viscometer at 25 ℃, specific gravity was measured with a hydrometer and multiplied by two values to calculate the viscosity.

2. Pretilt angle

It was measured by the crystal rotation method using He-Ne laser 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 the 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 a voltage of 5 V was applied 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 Example 3 and Comparative Example 1 of the present invention are shown as Table 1 below. In addition, photographs before and after exposure are shown in FIGS. 1 and 2.

division Pretilt Voltage retention rate Orientation Before exposure After exposure Example 3 89 ° 99% Bad Good Comparative Example 1 89 ° 99% Bad Bad

1 shows a liquid crystal alignment photograph of the liquid crystal display device manufactured by Example 3 of the present invention. In Fig. 1, the left side is before exposure and the right side is after exposure.

2 shows a liquid crystal alignment photograph of the liquid crystal display device manufactured by Comparative Example 1. FIG. In Fig. 2, the left side is before exposure and the right side is after exposure.

Referring to Table 1, Figures 1 and 2, it was confirmed that the liquid crystal display device manufactured according to the embodiment of the present invention exhibits excellent properties compared to the liquid crystal display device according to the comparative example because of the good post-exposure properties. In addition, the liquid crystal display device manufactured according to the embodiment of the present invention can be confirmed that the domain after the exposure is not observed at all, the alignment state is excellent, but the liquid crystal display device of the comparative example is poor in the alignment state because the domain difference before and after exposure is small I could confirm it.

Claims (12)

A photoactive crosslinker compound represented by formula (I)
(I)

In Formula I,
At least one of X ₁ , X ₂ , X _3, and X ₄

And the rest is H;
R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;
A is

or

ego;
B is

or

;
n is an integer from 1 to 20.
The method of claim 1,
Wherein the compound of Formula I is selected from the group consisting of compounds represented by the following Formulas 20, 22 and 24:
[Chemical Formula 20]

[Chemical Formula 22]

[Formula 24]

In Chemical Formulas 20, 22 and 24,
R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group; n is an integer from 1 to 20.
A photoactive crosslinking compound represented by the following formula (II):
[Formula II]

In the above formula (II)
At least one of X ₁ , X ₂ , X _3, and X ₄

And the rest is H;
R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;
A is

or

ego;
B is

or

;
n is an integer from 1 to 20.
The method of claim 3, wherein
The compound of Formula II is a photoactive crosslinking compound represented by the following Formula 40:
(40)

In Chemical Formula 40,
R ₁ To R ₄ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group; n is an integer from 1 to 20.
The photoactive crosslinking agent compound according to any one of claims 1 to 4; And
Liquid crystal aligning agent containing polyamic acid or polyimide.
The liquid crystal aligning agent of Claim 5 containing 0.1-40 weight part of said photoactive crosslinking agent compounds with respect to 100 weight part of said polyamic acids or polyimide.
The liquid crystal aligning agent according to claim 5, wherein the polyamic acid is prepared by reacting a diamine compound and tetracarboxylic anhydride.
The method of claim 7, wherein the diamine compound is p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-dia Minodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-dia Minodiphenylether, 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'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4 -Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- ratio (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 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'-dia Mino-5,5'-dimethoxybiphenyl, 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] hexafluoropropane, 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, di (4 -Aminophenyl) benzidine, 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 1,1-methaxylylenediamine, 1,3-propanediamine, tetramethylene Diamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine , Octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4 '-Methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 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- Diaminopurine, 5,6-diamino-1,3-dimethylura , 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4- Diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide and 1- (3,5- Liquid crystal aligning agent containing 1 or more types chosen from the group which consists of diaminophenyl) -3-octadecyl succinimide.
The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 5.
The liquid crystal display element provided with the liquid crystal aligning film of Claim 9.
A method for preparing a photoactive crosslinking compound represented by the following Formula 20, comprising reacting a compound represented by the following Formula 19 with a compound represented by the following Formula 5:
[Chemical Formula 19]

[Chemical Formula 5]

[Chemical Formula 20]

In Chemical Formulas 5, 19 and 20,
R ₁ To R ₈ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;
n is an integer from 1 to 20.
A method of preparing a photoactive crosslinking compound represented by the following Chemical Formula 40, comprising reacting a compound represented by the following Chemical Formula 39 with a compound represented by the following Chemical Formula 28:
[Chemical Formula 39]

[Formula 28]

(40)

In Chemical Formulas 28, 39, and 40,
R ₁ To R ₄ is the same as or different from each other, and is each independently selected from the group consisting of H, CN, NO ₂ , CF ₃ , halogen, C 1 -C 10 alkyl group and C 1 -C 10 alkoxy group;
n is an integer from 1 to 20.

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