WO2015053505A1

WO2015053505A1 - Fluorinated phenyl-thiophene-based polymerizable mesogenic compound with improved solubility in host liquid crystal, preparation method therefor, and polymerizable liquid crystal composition containing same

Info

Publication number: WO2015053505A1
Application number: PCT/KR2014/009182
Authority: WO
Inventors: 가재원; 김진수; 이미혜; 김윤호; 장광석; 김희주; 최진욱; 이성규; 조성찬; 노경래
Original assignee: 주식회사 동진쎄미켐
Priority date: 2013-10-10
Filing date: 2014-09-30
Publication date: 2015-04-16
Also published as: KR101512173B1; CN105637064A; CN105637064B

Abstract

The present invention relates to: a fluorinated phenyl-thiophene-based polymerizable mesogenic compound with improved solubility in a host liquid crystal; a preparation method therefor; and a polymerizable liquid crystal composition containing the same. The phenyl-thiophene-based polymerizable mesogenic compound of the present invention increases the solubility in a vertically aligned host liquid crystal by asymmetrically introducing a fluorine group as a solubility-improving group to a phenyl-thiophene core and introduces a methacrylate as a photoreactive group, thereby improving the stability of a pretilt angle after photo-cross-linking, and thus can be useful as a polymerizable liquid crystal composition, particularly, a polymerizable liquid crystal composition for a polymer-stabilized alignment liquid crystal display.

Description

Fluorine-introduced phenyl-thiophene-based polymerizable mesogen compound with improved solubility in a host liquid crystal, a preparation method thereof and a polymerizable liquid crystal composition comprising the same

The present invention relates to a fluorine-introduced phenyl-thiophene-based polymerizable mesogen compound having improved solubility in a host liquid crystal, a method for preparing the same, and a polymerizable liquid crystal composition comprising the same.

As digitalization and informatization are accelerated, many IT (Information Technology) devices are being used in daily life, and display technology for this is being developed. The most representative electronic display used in the past is the CRT (Cathode Ray Tube) monitor used in TVs and computer monitors. However, since CRT monitors are bulky and heavy, they have difficulty in size and portability, have high power consumption, and are increasingly replaced by other flat panel displays due to high driving voltages.

Typical flat panel displays to overcome the limitations of CRT monitors include liquid crystal displays (LCDs), plasma display panels (PDPs) and organic light emitting diodes (OLEDs). The most common at present is liquid crystal display (LCD). Liquid crystal display (LCD), which combines liquid crystal and semiconductor technology, has the advantages of thin, light and low power consumption. Currently, large TV (Television), PC (Personal Computer) monitor, display device of various measuring devices, PMP (Portable Multimedia Player) In addition, it is widely applied to MP3 (Moving Picture Experts Group) -1 Audio Layer-3 (MPEG) devices, car navigation devices and mobile phones.

Generally liquid crystal displays include liquid crystal cells and polarizing plates. The polarizing plate consists of a protective film and a polarizing film, which can be prepared by laminating a polarizing film made of a polyvinyl alcohol film with iodine, stretching, and laminating both sides with a protective film. In the case of a transmissive liquid crystal display (LCD), the polarizing plates may be mounted on both sides of the liquid crystal cell, or may be manufactured by arranging an optical compensation sheet having one or more optically anisotropic layers. In the case of a reflective liquid crystal display (LCD), a reflective plate, a liquid crystal cell, one or more optical compensation sheets, and a polarizing plate may be disposed in the order of manufacturing. At this time, the liquid crystal cell is composed of liquid crystal molecules, two substrates for encapsulating it, and an electrode layer for applying a voltage to the liquid crystal molecules.

The liquid crystal cell can display ON / OFF due to the difference in the alignment state of the liquid crystal molecules, and can be applied to both the transmissive type and the reflective type, so that TN (Twisted nematic), IPS (in-plane switching), and OCB (Optically Compensatory Bend) Various types of liquid crystal displays have been developed, such as Vertically Aligned (VA), Electrically Controlled Birefringence (ECB), and Super Twisted Nematic (STN). In addition, each of these types has a unique liquid crystal array and has inherent optical anisotropy. Therefore, in order to compensate for the change in the optical axis of linearly polarized light due to the optical anisotropy of these liquid crystal types, various optical anisotropy compensation films are required.

In order to compensate the optical anisotropy of such a liquid crystal form, the liquid crystal compound which has a polymeric group can be applied to optical elements, such as a polarizing plate and a retardation plate. Such an optical element can be obtained by polymerizing a polymerizable liquid crystal having optical anisotropy in a liquid crystal state and immobilizing the polymer liquid crystal. The polymerizable liquid crystal thus prepared can be polymerized while maintaining an alignment state by performing proper alignment control in a liquid crystal state. Can be. Therefore, a polymer having various optical anisotropy can be obtained by fixing the alignment state of the liquid crystal skeleton to a state such as homogeneous alignment, hybrid alignment, oblique alignment, homeotropic alignment, twist alignment, or the like. In addition, the liquid crystal compound having a polymerizable group is a polymer stabilized alignment (PSA: Polymer Stabilized Aligned) or a polymer stabilized vertical alignment (PS-VA) among VA type liquid crystal displays widely used in high-end monitors and large TVs. Can be used for liquid crystal displays.

A liquid crystal display liquid crystal cell of the conventional VA type includes a host liquid crystal having negative dielectric anisotropy between two transparent electrodes, and in the off state where no voltage is applied, these liquid crystal molecules are oriented perpendicular to the electrode surface. In the on state where a voltage is applied to the electrode, the liquid crystal molecules are aligned parallel to the electrode surface. The opening and closing of the light from the backlight passing through the polarizer can be controlled according to the vertical and horizontal alignment of the liquid crystal according to the presence or absence of voltage, but the response speed is very high if the direction of parallel alignment when the voltage is applied to the electrode is not determined in advance. There are disadvantages.

Meanwhile, PSA or PS-VA, which is one of VA types, is a method for controlling the inclination of vertically aligned liquid crystals in a liquid crystal cell, and mixes a mesogenic compound that can be polymerized by ultraviolet rays with a host liquid crystal in the liquid crystal cell. . In this case, the photoreactive mesogen compound to be used must move together in the direction in which the host liquid crystal lies when voltage is applied to the electrode through interaction with the vertically aligned liquid crystal. When the induction is inclined and then cured through light irradiation, a constant inclination is maintained even when no voltage is applied. When the voltage is applied again, the host liquid crystal is rapidly oriented in the inclination direction, thereby realizing a high-speed response.

The polymerizable mesogen compound used in the PSA or PS-VA type liquid crystal display must not only have high photoreaction efficiency but also have high solubility with the host liquid crystal because the liquid crystal cell is prepared by mixing with the host liquid crystal. Furthermore, an appropriate core is required to provide stability to the pretilt angle of the mesogen compound inclined in the lying direction of the host liquid crystal.

Accordingly, studies on polymerizable mesogenic compounds for liquid crystal displays of PSA or PS-VA type have been actively conducted, and the results are recently published one after another.

First, a liquid crystal display device comprising an alignment film having an alignment base film oriented to have a pretilt and a double layer of an alignment control film having a polymerized mesogen represented by the following formula (Patent Document 1):

P ₁ -A _1- (Z ₁ -A ₂ ) n-P ₂

(Wherein

P ₁ and P ₂ are independently selected from acrylate, methacrylate and the like; And

A ₁ and A ₂ are independently selected from 1,4-phenylene and naphthalene-2,6-diyl).

Next, a novel mesogen compound represented by the following formula has been disclosed (Patent Document 2):

Where X is

,

And the like).

Next, there has been disclosed a polymer stabilized liquid crystal composition characterized by containing a compound represented by the following formula (Patent Document 3 and Patent Document 4):

However, there has been no report on the phenyl-thiophene-based polymerizable mesogen compound and its polymerizable liquid crystal composition including the same, which have introduced a fluorine group and improved solubility.

Accordingly, the present inventors have been researching with interest for mesogenic compounds having high photoreaction efficiency, and the phenyl-thiophene-based polymerizable mesogen compound having a fluorine group is excellent in solubility in host liquid crystals, and thus photocrosslinking is possible. The present invention has been completed by revealing that it can be usefully used as a polymerizable liquid crystal composition for liquid crystal display of polymer stabilized alignment type since it has an effect of improving the stability of the post-tilt angle.

[Preceding technical literature]

[Patent Documents]

Republic of Korea Patent Publication No. 2011-0104416;

Republic of Korea Patent Application Publication No. 2011-0094944;

Republic of Korea Patent Publication No. 2009-0014375;

Republic of Korea Patent Publication No. 2010-0848116.

An object of the present invention is to provide a phenyl-thiophene-based polymerizable mesogenic compound with improved solubility in the host liquid crystal.

Another object of the present invention is to provide a method for preparing the phenyl-thiophene-based polymerizable mesogen compound.

Another object of the present invention is to provide a polymerizable liquid crystal composition comprising the phenyl-thiophene-based polymerizable mesogen compound.

It is also an object of the present invention to provide a polymer stabilized aligned liquid crystal display having a liquid crystal layer containing the polymerizable liquid crystal composition.

In order to achieve the above object,

The present invention provides a phenyl-thiophene-based polymerizable mesogenic compound represented by Formula 1 below:

[Formula 1]

(In Formula 1, R ¹ , R ² , R ³ , R ⁴ and X are as described herein).

In addition, the present invention as shown in Scheme 1,

A phenyl-thiophene-based polymerizable mesogenic compound represented by Chemical Formula 1, which comprises dissolving a compound represented by Chemical Formula 8 and a compound represented by Chemical Formula 9 in an organic solvent and then reacting to prepare a compound represented by Chemical Formula 1. Provides a method for preparing:

Scheme 1

(In Reaction Scheme 1, R ¹ , R ² , R ³ , R ⁴ and X are as defined herein).

Furthermore, the present invention provides a polymerizable liquid crystal composition comprising a phenyl-thiophene-based polymerizable mesogen compound represented by Chemical Formula 1.

Also provided is a polymer stabilized alignment liquid crystal display comprising a liquid crystal layer containing the polymerizable liquid crystal composition of the present invention.

The phenyl-thiophene-based polymerizable mesogen compound of the present invention is asymmetrically introduced into the phenyl-thiophene core as a solubility enhancer to increase the solubility for the vertically aligned host liquid crystal and to introduce methacrylate as a photoreactive group. Since there is an effect of improving the stability of the pretilt angle after light crosslinking, it can be usefully used as a polymerizable liquid crystal composition, in particular, a polymerizable liquid crystal composition for liquid crystal display of the polymer stabilized alignment type.

1 is a photograph taken after dissolving the phenyl-thiophene-based polymerizable mesogen compound of Examples 1 to 6 according to the present invention in MLC-6608 (Merck, Inc.), which is a vertically aligned host liquid crystal.

Hereinafter, the present invention will be described in detail.

Formula 1

In Chemical Formula 1,

X is O, NH or S;

R ¹ , R ² , R ³ and R ⁴ are independently hydrogen or fluorine (F), wherein at least one of them is fluorine.

Preferably, the phenyl-thiophene-based polymerizable mesogenic compound represented by Formula 1 is any one selected from the group consisting of compounds represented by Formulas 2 to 7:

Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

Formula 7

In Chemical Formulas 2 to 7, X is O, NH or S.

More preferably, the phenyl-thiophene-based polymerizable mesogen compound represented by the formula (1) is a compound in which the substituent X of the compound represented by the formulas (2) to (7) is O.

In addition, the present invention as shown in Scheme 1,

Scheme 1

In Reaction Scheme 1,

X is O, NH or S;

Hereinafter, a method for preparing the phenyl-thiophene-based polymerizable mesogen compound according to the present invention will be described in detail.

Specifically, in the method for preparing a phenyl-thiophene-based polymerizable mesogen compound according to the present invention, a compound represented by Chemical Formula 1 by dissolving a compound represented by Chemical Formula 8 and a compound represented by Chemical Formula 9 in an organic solvent and reacting It can manufacture.

In the production method according to the invention, the organic solvent may be carried out under a conventional organic solvent. Any solvent capable of dissolving each reactant well may be selected and used without limitation, and may be used alone or in combination. At this time, as the organic solvent, for example, dichloromethane (DCM), dimethylformamide (DMF), dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and the like. It is possible to use, preferably dichloromethane (DCM) can be used.

In the production method according to the present invention, in order to improve the reaction activity or the reaction rate, it may be reacted by further adding a base catalyst as needed. The base catalyst may be any conventional base as long as it is a base capable of improving reaction activity or reaction rate, and preferably, ammonia, pyridine, trimethylamine (TMA), and triethylamine (TEA). ), Dimethylamine (DMA), diethylamine (DEA), N, N-diisopropylethylamine (DIPEA), N-methylporporin, N-methylpiperidine, N, N-dimethylaniline, di Methylaminopyridine (DMAP), tetramethylethylenediamine (TMEDA) and the like can be used, and preferably N, N-dimethylaminopyridine (DMAP) can be used.

Furthermore, the present invention provides a polymerizable liquid crystal composition comprising a polymerizable mesogenic compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

X is O, NH or S;

The present invention also provides a polymer stabilized alignment liquid crystal display having a liquid crystal layer comprising the polymerizable liquid crystal composition.

In this case, the polymer stabilized alignment liquid crystal display according to the present invention is preferably a liquid crystal display of vertical alignment type (VA-MODE).

As a result of evaluating the solubility with the host liquid crystal in order to apply the phenyl-thiophene-based polymerizable mesogen compound into which the fluorine group according to the present invention is introduced to the stabilized alignment liquid crystal display, the fluorine groups of Examples 1 to 6 according to the present invention were introduced. The phenyl-thiophene-based polymerizable mesogen compound was found to have significantly improved solubility in the vertically aligned host liquid crystal even at room temperature (see Experimental Example 1).

Therefore, the phenyl-thiophene-based polymerizable mesogen compound into which the fluorine group is introduced according to the present invention has a remarkably excellent solubility in the host liquid crystal, and thus the polymerizable liquid crystal composition for liquid crystal display of the polymer stabilized alignment type controlling the inclination of the host liquid crystal It can be usefully used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.

However, the following Examples and Experimental Examples are only illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

<제조예 1> 5-(4’-메톡시페닐)-2-(피나콜보로닐)싸이오펜 합성Preparation Example 1 Synthesis of 5- (4′-methoxyphenyl) -2- (pinacolboronyl) thiophene

Step 1: 2- (4'-methoxyphenyl) thiophene synthesis

To a solution of 2-bromothiophene (2.0 g, 12.3 mmol) in xylene (50 mL), an aqueous potassium carbonate solution (2M, 20 mL) was added, followed by 4-methoxy dissolved in ethanol (35 mL). Phenylboronic acid (4.7 g, 30.7 mmol) was added thereto and degassed for 30 minutes. Tetrakis (triphenylphosphine) palladium (1.4 g, 1.2 mmol) was added to the mixed solution, and the mixture was refluxed for 24 hours. Excess distilled water was added to the reaction solution to terminate the reaction, followed by extraction with dichloromethane and concentration of the solvent under reduced pressure. The obtained residue was purified by column chromatography to give a white solid compound (2.2 g, 94%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.61 (m, 2H), 7.36-7.30 (m, 2H), 7.09 (m, 1H), 7.06 (m, 2H), 3.82 (3H, s); MS m / z 190 (M ⁺ )

Step 2: 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene synthesis

2- (4'-methoxyphenyl) thiophene (3.0 g, 15.8 mmol) prepared in step 1 was dissolved in tetrahydrofuran (100 ml), followed by tetramethylethylenediamine (TMEDA, 2.4 ml, 15.8). mmol) was added and the reaction temperature was reduced to -78 ° C. Butyl lithium (n-BuLi, 19.7 mL, 1.6M, 31.5 mmol) was slowly added dropwise to the mixed solution, the reaction temperature was raised to 0 ° C. and stirred for 1 hour. Next, the reaction temperature was lowered to −78 ° C., and bis (pinacolato) diborone (4.8 g, 18.9 mmol) was dissolved in tetrahydrofuran (30 mL), added to the reaction solution, and then heated at room temperature for 12 hours. Was stirred. Saturated sodium bicarbonate aqueous solution (600 mL) was added to the reaction solution to terminate the reaction, and extracted with dichloromethane. After distilling off the solvent under reduced pressure, the residue was separated by column chromatography (hexane: dichloromethane = 50: 1) to give a blue solid compound (2.8 g, 28%).

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.58-7.55 (m, 3H), 7.27 (d, 1H), 6.92 (d, 2H), 3.82 (s, 3H), 1.35 (s, 12H); MS m / z 316 (M ⁺ )

<제조예 2> 5-(4’-메톡시페닐)-2-(4’-메톡시-3’,5’-디플로로페닐)싸이오펜 합성Preparation Example 2 Synthesis of 5- (4'-methoxyphenyl) -2- (4'-methoxy-3 ', 5'-difluorophenyl) thiophene

4-Bromo-2,6-difluoroanisole (500 mg, 1.6 mmol) was dissolved in dimethyl ether (10 mL), and saturated aqueous potassium carbonate solution (3 mL) was added thereto. 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene (506 mg, 1.6 mmol) prepared in Preparation Example 1 was dissolved in methanol (5 mL) and added to the mixed solution. After degassing for 30 minutes, tetrakis (triphenylphosphine) palladium (183 mg, 0.2 mmol) was added and refluxed for 12 hours. Excess distilled water was added to the reaction solution, and the resulting solid compound was filtered off. The resulting mixture was separated by column chromatography to give a pale yellow solid compound (410 mg, 78%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.63 (d, 2H), 7.57 (d, 1H), 7.48 (d, 2H), 7.42 (d, 1H), 7.02 (d, 2H), 3.95 ( s, 3H), 3.80 (s, 3H); MS m / z 332 (M ⁺ )

<제조예 3> 5-(4’-메톡시페닐)-2-(4’-메톡시-2’,3’-디플로로페닐)싸이오펜 합성Preparation Example 3 5- (4'-methoxyphenyl) -2- (4'-methoxy-2 ', 3'-difluorophenyl) thiophene synthesis

4-Bromo-2,3-difluoroanisole (1.56 g, 5.0 mmol) was dissolved in dimethyl ether (10 mL), and saturated aqueous potassium carbonate solution (5 mL) was added thereto. 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene (1.4 g, 4.55 mmol) prepared in Preparation Example 1 was dissolved in methanol (10 mL) and added to the mixed solution. After degassing for 30 minutes, tetrakis (triphenylphosphine) palladium (263 mg, 0.23 mmol) was added and refluxed for 12 hours. Excess distilled water was added to the reaction solution, and after completion of the reaction, the resulting solid compound was obtained by filtration. The resulting mixture was separated by column chromatography to give a pale yellow solid compound (1.2 g, 80%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.64 (d, 2H), 7.53 (m, 1H), 7.35 (s, 2H), 7.01 7.07 (m, 3H), 3.95 (s, 3H), 3.80 (s, 3H); MS m / z 332 (M ⁺ )

<제조예 4> 5-(4’-메톡시페닐)-2-(4’-메톡시-2’,3’-디플로로페닐)싸이오펜 합성Production Example 4 5- (4'-methoxyphenyl) -2- (4'-methoxy-2 ', 3'-difluorophenyl) thiophene synthesis

4-Bromo-3,5-difluoroanisole (1.56 g, 5.0 mmol) was dissolved in dimethyl ether (10 mL), and saturated aqueous potassium carbonate solution (5 mL) was added thereto. 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene (1.4 g, 4.55 mmol) prepared in Preparation Example 1 was dissolved in methanol (10 mL) and added to the mixed solution. After degassing for 30 minutes, tetrakis (triphenylphosphine) palladium (263 mg, 0.23 mmol) was added and refluxed for 12 hours. Excess distilled water was added to the reaction solution, and after completion of the reaction, the resulting solid compound was obtained by filtration. The resulting mixture was separated by column chromatography to give a pale yellow solid compound (1.1 g, 78%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.62 (d, 2H), 7.43 (s, 2H), 7.10 (d, 2H), 6.68 (d, 2H), 3.97 (s, 6H); MS m / z 332 (M ⁺ )

<제조예 5> 5-(4’-메톡시페닐)-2-(4’-메톡시-3’-플로로페닐)싸이오펜 합성Production Example 5 5- (4'-methoxyphenyl) -2- (4'-methoxy-3'-fluorophenyl) thiophene synthesis

4-Bromo-2-fluoroanisole (713 mg, 3.16 mmol) was dissolved in dimethyl ether (10 mL), and then saturated aqueous potassium carbonate solution (5 mL) was added thereto. 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene (1.0 g, 3.16 mmol) prepared in Preparation Example 1 was dissolved in methanol (10 mL) and added to the mixed solution. After degassing for 30 minutes, tetrakis (triphenylphosphine) palladium (183 mg, 0.16 mmol) was added and refluxed for 12 hours. Excess distilled water was added to the reaction solution, and after completion of the reaction, the resulting solid compound was obtained by filtration. The resulting mixture was separated by column chromatography to give a pale yellow solid compound (795 mg, 80%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.63 (d, 2H), 7.53 (m, 2H), 7.35 (m, 3H), 7.03 (d, 2H), 3.81 (m, 6H); MS m / z 314 (M ⁺ )

<제조예 6> 5-(4’-메톡시페닐)-2-(4’-메톡시-2’-플로로페닐)싸이오펜 합성Preparation Example 6 5- (4'-methoxyphenyl) -2- (4'-methoxy-2'-fluorophenyl) thiophene synthesis

4-Bromo-3-fluoroanisole (713 mg, 3.16 mmol) was dissolved in dimethyl ether (10 mL), and then saturated aqueous potassium carbonate solution (5 mL) was added thereto. 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene (1.0 g, 3.16 mmol) prepared in Preparation Example 1 was dissolved in methanol (10 mL) and added to the mixed solution. After degassing for 30 minutes, tetrakis (triphenylphosphine) palladium (183 mg, 0.16 mmol) was added and refluxed for 12 hours. Excess distilled water was added to the reaction solution, and after completion of the reaction, the resulting solid compound was obtained by filtration. The resulting mixture was separated by column chromatography to give a pale yellow solid compound (804 mg, 83%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.77 (m, 3H), 7.31 (s, 2H), 7.03 (d, 2H), 6.82 (m, 2H), 3.80 (m, 6H); MS m / z 314 (M ⁺ )

<제조예 7> 5-(4’-메톡시페닐)-2-(4’-메톡시-2’,3’,5’,6’-테트라플로로페닐)싸이오펜 합성Production Example 7 5- (4'-methoxyphenyl) -2- (4'-methoxy-2 ', 3', 5 ', 6'-tetrafluorophenyl) thiophene synthesis

4-Bromo-2,3,5,6-tetrafluoroanisole (901 mg, 3.48 mmol) was dissolved in dimethyl ether (10 mL), followed by saturated aqueous potassium carbonate solution (5 mL). 5- (4'-methoxyphenyl) -2- (pinacolboronyl) thiophene (1.0 g, 3.16 mmol) prepared in Preparation Example 1 was dissolved in methanol (10 mL) and added to the mixed solution. After degassing for 30 minutes, tetrakis (triphenylphosphine) palladium (183 mg, 0.16 mmol) was added and refluxed for 12 hours. Excess distilled water was added to the reaction solution, and after completion of the reaction, the resulting solid compound was obtained by filtration. The resulting mixture was separated by column chromatography to give a pale yellow solid compound (815 mg, 70%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ7.64 (d, 2H), 7.39 (s, 2H), 7.02 (d, 2H), 3.91 (m, 6H); MS m / z 368 (M ⁺ )

<실시예 1> 2-(3’,5’-디플로로-4’-메타아크릴로익옥시페닐)-5-(4’’-메타아크릴로익옥시페닐) 싸이오펜 합성<Example 1> 2- (3 ', 5'-difluoro-4'-methacryloicoxyphenyl) -5- (4' '-methacryloicoxyphenyl) thiophene synthesis

5- (4'-methoxyphenyl) -2- (4'-methoxy-3 ', 5'-difluorophenyl) thiophene (500 mg, 1.51 mmol) prepared in Preparation Example 2 was diluted with After dissolving in methane (20 mL), tribromoborane (1.5 g, 6.02 mmol) dissolved in dichloromethane (5 mL), cooled to -78 ° C, was slowly added dropwise. The reaction solution was stirred for 20 minutes, and then stirred at room temperature for 4 hours. Next, methanol was added to the reaction solution to decompose an excess of tribromoborane, an excess of distilled water was added, and the resulting precipitate was filtered and washed with distilled water. The resulting compound was dried in a vacuum oven and dissolved in dichloromethane (10 mL), followed by triethylamine (2 mL), 4- (N, N-dimethylamino) pyridine (184 mg, 1.51 mmol) and methacryl. One chloride (394 mg, 3.77 mmol) was added dropwise and stirred at room temperature for 3 hours. Excess distilled water was added to the reaction solution to terminate the reaction, acidified with 3N hydrochloric acid (pH 2 to 3), extracted with dichloromethane, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to give a white solid (517 mg, 78%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.81 (d, 2H), 7.65 (d, 1H), 7.56-7.51 (m, 3H), 7.30 (d, 2H), 6.45 (s, 1H), 6.34 (s, 1 H), 6.02 (s, 1 H), 5.88 (s, 1 H), 2.10-2.05 (m, 6 H); MS m / z 440 (M ⁺ )

<실시예 2> 2-(2’,3’-디플로로-4’-메타아크릴로익옥시페닐)-5-(4’’-메타아크릴로익옥시페닐) 싸이오펜 합성<Example 2> 2- (2 ', 3'-difluoro-4'-methacryloicoxyphenyl) -5- (4' '-methacryloicoxyphenyl) thiophene synthesis

5- (4'-methoxyphenyl) -2- (4'-methoxy-2 ', 3'-difluorophenyl) thiophene (500 mg, 1.51 mmol) prepared in Preparation Example 3 was diluted with After dissolving in methane (20 mL), tribromoborane (1.5 g, 6.02 mmol) dissolved in dichloromethane (5 mL), cooled to -78 ° C, was slowly added dropwise. The reaction solution was stirred for 20 minutes, and then stirred at room temperature for 4 hours. Next, methanol was added to the reaction solution to decompose an excess of tribromoborane, an excess of distilled water was added, and the resulting precipitate was filtered and washed with distilled water. The resulting compound was dried in a vacuum oven and dissolved in dichloromethane (10 mL), followed by triethylamine (2 mL), 4- (N, N-dimethylamino) pyridine (184 mg, 1.51 mmol) and methacryl. One chloride (394 mg, 3.77 mmol) was added dropwise and stirred at room temperature for 3 hours. Excess distilled water was added to the reaction solution to terminate the reaction, acidified with 3N hydrochloric acid (pH 2 to 3), extracted with dichloromethane, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to obtain a white solid (620 mg, 81%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.78 (d, 2H), 7.51 (m, 1H), 7.33 (s, 2H), 7.15-7.30 (m, 3H), 6.45 (s, 1H), 6.33 (s, 1 H), 6.02 (s, 1 H), 5.90 (s, 1 H), 2.10-2.05 (m, 6 H); MS m / z 440 (M ⁺ )

<실시예 3> 2-(2’,6’-디플로로-4’-메타아크릴로익옥시페닐)-5-(4’’-메타아크릴로익옥시페닐) 싸이오펜 합성<Example 3> 2- (2 ', 6'-difluoro-4'-methacryloicoxyphenyl) -5- (4' '-methacryloicoxyphenyl) thiophene synthesis

5- (4'-methoxyphenyl) -2- (4'-methoxy-2 ', 6'-difluorophenyl) thiophene (500 mg, 1.51 mmol) prepared in Preparation Example 4 was diluted with After dissolving in methane (20 mL), tribromoborane (1.5 g, 6.02 mmol) dissolved in dichloromethane (5 mL), cooled to -78 ° C, was slowly added dropwise. The reaction solution was stirred for 20 minutes, and then stirred at room temperature for 4 hours. Next, methanol was added to the reaction solution to decompose an excess of tribromoborane, an excess of distilled water was added, and the resulting precipitate was filtered and washed with distilled water. The resulting compound was dried in a vacuum oven and dissolved in dichloromethane (10 mL), followed by triethylamine (2 mL), 4- (N, N-dimethylamino) pyridine (184 mg, 1.51 mmol) and methacryl. One chloride (394 mg, 3.77 mmol) was added dropwise and stirred at room temperature for 3 hours. Excess distilled water was added to the reaction solution to terminate the reaction, acidified with 3N hydrochloric acid (pH 2 to 3), extracted with dichloromethane, the solvent was distilled off under reduced pressure, white column (500 mg, 75%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.80 (d, 2H), 7.59-7.65 (m, 3H), 7.30 (d, 2H), 6.45 (s, 1H), 6.34 (s, 1H), 6.02 (s, 1 H), 5.88 (s, 1 H), 2.08 (m, 6 H); MS m / z 440 (M ⁺ )

<실시예 4> 2-(3’-플로로-4’-메타아크릴로익옥시페닐)-5-(4’’-메타아크릴로익옥시페닐) 싸이오펜 합성<Example 4> 2- (3'-fluoro-4'-methacryloicoxyphenyl) -5- (4 ''-methacryloicoxyphenyl) thiophene synthesis

5- (4'-methoxyphenyl) -2- (4'-methoxy-3'-fluorophenyl) thiophene (1.0 g, 3.18 mmol) prepared in Preparation Example 5 was diluted with dichloromethane (20 mL ), Tribromoborane (1.5 g, 6.02 mmol) dissolved in dichloromethane (5 mL), cooled to -78 ° C, was slowly added dropwise. The reaction solution was stirred for 20 minutes, and then stirred at room temperature for 4 hours. Next, methanol was added to the reaction solution to decompose an excess of tribromoborane, an excess of distilled water was added, and the resulting precipitate was filtered and washed with distilled water. The obtained compound was dried in a vacuum oven and dissolved in dichloromethane (10 mL), and then triethylamine (2 mL), 4- (N, N-dimethylamino) pyridine (389 mg, 3.18 mmol) and methacryl One chloride (831 mg, 7.95 mmol) was added dropwise and stirred at room temperature for 3 hours. Excess distilled water was added to the reaction solution to terminate the reaction, acidified with 3N hydrochloric acid (pH 2 to 3), extracted with dichloromethane, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to obtain a white solid (1.06 g, 79%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.75 (d, 2H), 7.48 (m, 2H), 7.50 (m, 3H), 7.21 (d, 2H), 6.43 (s, 1H), 6.34 ( s, 1H), 6.02 (s, 1H), 5.88 (s, 1H), 2.10-2.05 (m, 6H); MS m / z 422 (M ⁺ )

<실시예 5> 2-(2’-플로로-4’-메타아크릴로익옥시페닐)-5-(4’’-메타아크릴로익옥시페닐) 싸이오펜 합성<Example 5> 2- (2'-fluoro-4'-methacryloicoxyphenyl) -5- (4 ''-methacryloicoxyphenyl) thiophene synthesis

5- (4'-methoxyphenyl) -2- (4'-methoxy-2'-fluorophenyl) thiophene (1.0 g, 3.18 mmol) prepared in Preparation Example 6 was diluted with dichloromethane (20 mL). ), Tribromoborane (3.19 g, 12.72 mmol) dissolved in dichloromethane (1 mL), cooled to -78 ° C, was slowly added dropwise. The reaction solution was stirred for 20 minutes, and then stirred at room temperature for 4 hours. Next, methanol was added to the reaction solution to decompose an excess of tribromoborane, an excess of distilled water was added, and the resulting precipitate was filtered and washed with distilled water. The obtained compound was dried in a vacuum oven and dissolved in dichloromethane (10 mL), and then triethylamine (2 mL), 4- (N, N-dimethylamino) pyridine (389 mg, 3.18 mmol) and methacryl One chloride (831 mg, 7.95 mmol) was added dropwise and stirred at room temperature for 3 hours. Excess distilled water was added to the reaction solution to terminate the reaction, acidified with 3N hydrochloric acid (pH 2-3), extracted with dichloromethane, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography to obtain a white solid (1.2 g, 81%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.71 (m, 3H), 7.49 (m, 2H), 7.42 (s, 2H), 7.20 (d, 2H), 7.05 (m, 1H), 6.44 ( s, 1H), 6.34 (s, 1H), 6.02 (s, 1H), 5.88 (s, 1H), 2.11-2.05 (m, 6H); MS m / z 422 (M ⁺ )

<실시예 6> 2-(2’,3’,5’6’-테트라플로로-4’-메타아크릴로익옥시페닐)-5-(4’’-메타아크릴로익옥시페닐) 싸이오펜 합성Example 6 2- (2 ', 3', 5'6'-tetrafluoro-4'-methacryloicoxyphenyl) -5- (4 ''-methacryloicoxyphenyl) thiophene synthesis

5- (4'-methoxyphenyl) -2- (4'-methoxy-2 ', 3', 5 ', 6'-tetrafluorophenyl) thiophene prepared in Preparation Example 7 (500 mg, 1.36 mmol) was dissolved in dichloromethane (20 mL), and then tribromoborane (1.4 g, 5.43 mmol) dissolved in dichloromethane (5 mL) cooled to -78 ° C was slowly added dropwise. The reaction solution was stirred for 20 minutes, and then stirred at room temperature for 4 hours. Next, methanol was added to the reaction solution to decompose an excess of tribromoborane, an excess of distilled water was added, and the resulting precipitate was filtered and washed with distilled water. The obtained compound was dried in a vacuum oven and dissolved in dichloromethane (10 mL), followed by triethylamine (2 mL), 4- (N, N-dimethylamino) pyridine (166 mg, 1.36 mmol) and methacryl. One chloride (394 mg, 3.77 mmol) was added dropwise and stirred at room temperature for 3 hours. Excess distilled water was added to the reaction solution to terminate the reaction, acidified with 3N hydrochloric acid (pH 2 to 3), extracted with dichloromethane, the solvent was distilled off under reduced pressure, white column (530 mg, 82%).

¹ H NMR (300 MHz, acetone-d ₆ ) δ 7.70 (d, 2H), 7.35 (s, 2H), 7.11 (d, 2H), 6.43 (m, 2H), 6.08 (m, 2H), 2.06 ( m, 6H); MS m / z 476 (M ⁺ )

<실험예 1> 본 발명에 따른 중합성 메조겐 화합물의 호스트 액정과의 용해성 평가Experimental Example 1 Evaluation of Solubility of the Polymerizable Mesogen Compound According to the Present Invention with Host Liquid Crystal

In order to evaluate the solubility of the host liquid crystal and solubility of the phenyl-thiophene-based polymerizable mesogen compound into which the fluorine group of the present invention was introduced, the following experiment was performed.

Specifically, in order to evaluate solubility at room temperature, 0.5 wt% of each of the phenyl-thiophene-based polymerizable mesogen compounds prepared in Examples 1 to 6 was mixed and stirred with a host liquid crystal (MLC-6608, Merck) for vertical alignment. After that, the mixture was left at room temperature for 1 hour and then visually observed. In addition, 0.5% by weight of each of the polymerizable mesogenic compounds prepared in Examples 1 to 6 was mixed with the liquid crystal for vertical alignment (MLC-6608, Merck) for stirring at low temperature, and then stirred at -30 ° C. Changes were visually observed after standing for 3 days. The polymerizable mesogenic compounds of Examples 1 to 6 are photographed whether they are dissolved with the host liquid crystal, and are shown in FIG. 1 and visually observed to melt very well-(◎), when slightly heated to melt-(O) and If it does not melt-it is represented in Table 1 as indicated by (X).

1 is an image taken after dissolving the phenyl-thiophene-based polymerizable mesogen compound of Examples 1 to 6 in MLC-6608 (Merck, Inc.) which is a vertically aligned host liquid crystal.

Table 1

division	Room temperature	-30 ℃
Example 1	◎	◎
Example 2	◎	◎
Example 3	◎	◎
Example 4	◎	◎
Example 5	◎	◎
Example 6	◎	◎

As shown in Table 1 and FIG. 1, it was found that the phenyl-thiophene polymerizable mesogenic compound into which the fluorine group was introduced according to the present invention was remarkably excellent in solubility in the host liquid crystal at room temperature and -30 ° C. From this, it can be seen that the polymerizable mesogenic compounds of Examples 1 to 6 of the present invention have excellent solubility in the vertically aligned host liquid crystal due to the introduction of an asymmetric fluorine group.

Therefore, the phenyl-thiophene-based polymerizable mesogen compound incorporating the fluorine group of the present invention has excellent solubility with respect to the host liquid crystal, so that the polymerizable liquid crystal composition for liquid crystal display of polymer stabilized alignment type which controls the inclination of the host liquid crystal. It can be usefully used.

The phenyl-thiophene-based polymerizable mesogen compound incorporating the fluorine group of the present invention can be usefully used as a polymerizable liquid crystal composition for a liquid crystal display of a polymer stabilized alignment type that controls the inclination of a host liquid crystal.

Claims

Phenyl-thiophene-based polymerizable mesogenic compounds represented by Formula 1 below:

[Formula 1]

(In the above formula 1,

X is O, NH or S;

R 1 , R 2 , R 3 and R 4 are independently hydrogen or fluorine (F), wherein at least one of them is fluorine).
The method of claim 1,

The polymerizable mesogenic compound represented by Chemical Formula 1 is any one selected from the group consisting of compounds represented by the following Chemical Formulas 2, 3, 4, 5, 6, and 7-phenyl-thiophene-based polymerizable meso Gen compound:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

(In Formula 2 to Formula 7, X is O, NH, or S).
The method of claim 2,

Substituent X of Formulas 2 to 7 is O, phenyl-thiophene-based polymerizable mesogenic compound.
As shown in Scheme 1 below,

A phenyl-thiophene-based polymerizable mesogenic compound represented by Chemical Formula 1, which comprises dissolving a compound represented by Chemical Formula 8 and a compound represented by Chemical Formula 9 in an organic solvent and then reacting to prepare a compound represented by Chemical Formula 1. Manufacturing Method:

Scheme 1

(In Scheme 1, R 1 , R 2 , R 3 , R 4 and X are as described in claim 1).
The method of claim 4, wherein

The organic solvent is one selected from the group consisting of dichloromethane (DCM), dimethylformamide (DMF), dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) and tetrahydrofuran (THF) A process for producing a phenyl-thiophene-based polymerizable mesogen compound.
The method of claim 4, wherein

The preparation method is ammonia, pyridine, trimethylamine (TMA), triethylamine (TEA), dimethylamine (DMA), diethylamine (DEA), N, N-diisopropylethylamine (DIPEA ), N-methylporporin, N-methylpiperidine, N, N-dimethylaniline, dimethylaminopyridine (DMAP) and tetramethylethylenediamine (TMEDA) are at least one base catalyst selected from the group consisting of A method for producing a phenyl-thiophene-based polymerizable mesogen compound, which can be further added.
A polymerizable liquid crystal composition comprising a phenyl-thiophene-based polymerizable mesogen compound represented by Formula 1 below:

[Formula 1]

(In Formula 1, R 1 , R 2 , R 3 , R 4 and X are as described in claim 1).
A polymer stabilized alignment liquid crystal display having a liquid crystal layer comprising the polymerizable liquid crystal composition of claim 7.
The method of claim 8,

And said liquid crystal display is a liquid crystal display of vertical alignment type (VA-MODE).