KR20160126298A - hockey stic shaped reactive mesogen compound and method for preparing thereof - Google Patents

Abstract

More particularly, the present invention relates to a novel asymmetric hockey stick having a benzene number of 5 (5-ring) and having a fluorine substituent in benzene at one end thereof. The present invention relates to an asymmetric hockey stick reactive mesogen compound, Type reactive mesogenic compounds.
The asymmetric hocky stick type reactive mesogen compound of the present invention has excellent alignment properties of liquid crystal molecules and is free from optical defects such as light leakage and is suitable for the vertical alignment (VA) mode and realizes the next generation low voltage driving and high speed response display It is possible to use it as a source material for.

Description

Hockey stick type reactive mesogen compounds and methods for preparing the same

More particularly, the present invention relates to a novel asymmetric hockey stick having a benzene number of 5 (5-ring) and having a fluorine substituent in benzene at one end thereof. The present invention relates to an asymmetric hockey stick reactive mesogen compound, Type reactive mesogenic compounds.

Liquid crystal displays with liquid crystal and semiconductor technology are thin, light and low in power consumption. Because of these advantages, liquid crystal displays are leading the large display and TV market as well as computer monitors.

The latest LCD development and production is led by Korea. In particular, Samsung Electronics and LG Display are competing in the global market for the first and second in the world. In order to preoccupy the large-sized LCD market, we are investing a large amount of budget to expand the LCD line. In particular, this next-generation LCD production technology focuses on the development of large-screen LCD panels for fixed-line and smart TVs to be developed in the future.

In the global TV market, various displays (PDP, OLED, etc.) are in the fiercest competition. LCDs must meet high performance demands in order to lead the TV market. LCDs are rapidly responding to major performance factors that impede entry into the TV market, such as improved response speed, noticeable toughness, securing a wide viewing angle, and improved luminance. In the future, the demand for large-screen, high-definition, and 3D TVs is expected to grow dramatically due to income increase, full-scale digital broadcasting and home theater spreading. However, Speed and visibility, it does not meet the specifications required for full-HDTV flat panel displays.

(TN) mode, (2) IPS (In-Plane Switching) mode, or FFS (Fringe-Field Switching) mode, which can be divided into four groups according to how the initial nematic liquid crystal images are arranged. Mode, MVA (Multi-domain VA) and PVA (Patterned VA) mode, and OCB (Optically Compensated Bend) mode. As such, in the mass production of LCDs, the liquid crystal mode using the existing nematic phase is utilized, and the characteristics of the liquid crystal itself reaches the limit, so the performance for the next generation 3D LCD is not provided properly.

Flexoelectric or ferroelectric liquid crystals exhibiting macroscopic spontaneous polarization characteristics are one of the liquid crystal molecules that can meet the requirements of the fast response speed required in recent 3D TVs because they can exhibit fast electro-optical response characteristics. In the case of bent-nucleus liquid crystal molecules, it is one of the novel liquid crystal materials capable of having a high-speed response characteristic of several ms or less due to the anisotropy of the molecules themselves and the flexoelectricity characteristic macroscopically when the liquid crystal having such a molecular structure is oriented. The research on the existing flexoelectricity has mainly been focused on maximizing the flexoelectricity using the dopant in the existing nematic liquid crystals. Therefore, the improvement of the response speed that can be obtained was insignificant, the operating temperature range, the orientation characteristic, and the electro-optic effect were also inferior to commercialization.

Korean Patent Publication No. 10-2014-0107975

In order to solve the problems of the prior art as described above, the present invention provides a novel asymmetric hklocking reactive mesogen compound having five benzene rings and having a fluorine substituent at one end benzene, and a process for producing the same do.

Further, the present invention is suitable for a vertical alignment (VA) mode without optical defects such as light leakage due to excellent alignment properties of liquid crystal molecules, and can be used as a source material for realizing next generation low voltage driving and high speed response display It is another object of the present invention to provide a novel asymmetric hocky stick type reactive mesogen compound and a process for producing the same.

Another object of the present invention is to provide a liquid crystal composition, a liquid crystal orientation film, and a liquid crystal display device including the asymmetric hocky stick type reactive mesogen compound.

In order to achieve the above object, the present invention provides an asymmetric hklocking reactive mesogen compound represented by the following formula (1) having 5 benzene rings (5-rings) and having a fluorine substituent at one end benzene:

[Chemical Formula 1]

In Formula 1,

R is

or

And, wherein _{X 1, X 2, X 3} , X 4 and X ₅ are each independently H or F, wherein _{X 1, X 2, X 3} , X 4 and X _5, at least three or more of the F, Z M is an integer of 0 to 1, n is an integer of 3 to 5, and y is an integer of 3 to 12.

In particular, it is preferred that the asymmetric hklocking reactive mesogen compound is a compound represented by the following formula (1a) or (1b):

[Formula 1a]

[Chemical Formula 1b]

The present invention also relates to a process for preparing 4- (6- (acryloyloxy) hexyloxy) benzoic acid and 3- (3,4,5-trifluorophenylcarboxy) Which comprises reacting a phenyl 4- [4- (hydroxy) benzoyloxy] benzoate with 3- (3,4,5-trifluorophenyl carboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate. 1a. ≪ RTI ID = 0.0 > 1 < / RTI >

The present invention also provides a liquid crystal composition comprising the asymmetric hklocking reactive mesogen compound represented by Formula 1 above. At this time, the asymmetric hklocking reactive mesogen compound is preferably a compound represented by Formula 1a or 1b.

The liquid crystal composition preferably contains 1 to 10% by weight of the asymmetric hklocking reactive mesogen compound represented by the formula (1).

The present invention also provides a liquid crystal orientation film produced by coating the liquid crystal composition on a substrate and then photocuring.

The present invention also provides a liquid crystal display device comprising the liquid crystal alignment film.

The asymmetric hklocking reactive mesogen compound according to the present invention has excellent alignment properties of liquid crystal molecules and is free from optical defects such as light leakage and is suitable for application in the vertical alignment (VA) mode, and is suitable for next generation low voltage driving, It can be used as a source material for realization.

FIG. 1 is a graph showing the IR spectrum of a compound represented by formula (Ia) prepared according to an embodiment of the present invention.
FIG. 2 is a graph showing the ¹ H-NMR spectrum of the compound of formula (Ia) prepared according to an embodiment of the present invention.
FIG. 3 is a graph showing the IR spectrum of the compound of Formula 1b prepared according to an embodiment of the present invention. FIG.
FIG. 4 is a graph showing a ¹ H-NMR spectrum of a compound represented by formula (1b) prepared according to an embodiment of the present invention.
FIG. 5 is a graph showing the results of DSC thermal analysis of a compound represented by formula (Ia) according to an embodiment of the present invention.
FIG. 6 is a graph showing the results of DSC thermal analysis of a compound represented by the formula (1b) prepared according to an embodiment of the present invention.
FIGS. 7 and 8 are graphs showing the results of thermoelectric conversion measurement using a polarizing microscope of the compound represented by formula (Ia) according to an embodiment of the present invention.
FIGS. 9 and 10 are graphs showing the results of thermoelectric conversion measurement using a polarizing microscope of the compound represented by Formula 1b prepared according to an embodiment of the present invention. FIG.
FIG. 11 is a diagram showing the coating property measurement results of a compound represented by Formula 1a, a compound represented by Formula 1b, and a mixture of RM257 of Merck and a vertical aligning agent prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, asymmetric bending-nuclear mesogens are provided to make the structure of the liquid crystal molecules into an asymmetric bend shape, and acrylate and flexible lattice are introduced at the ends to synthesize bend-nucleus reactive liquid crystal monomers. Hockey stick type mesogen compounds were prepared by changing the type of polar groups and their properties were investigated.

The present invention provides a hocky stick type reactive mesogen compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R is

or

And, wherein _{X 1, X 2, X 3} , X 4 and X ₅ are each independently H or F, wherein _{X 1, X 2, X 3} , X 4 and X _5, at least three or more of the F, Z M is an integer of 0 to 1, n is an integer of 3 to 5, and y is an integer of 3 to 12.

In particular, the hocky stick type reactive mesogen compound of the present invention is preferably a compound represented by the following formula (1a) or (1b).

[Formula 1a]

[Chemical Formula 1b]

The compound represented by the above formula (1a) or (1b) has five benzenes (5-ring), fluorine atom is substituted for benzene at one end of five benzene, acrylate and flexible lattice are introduced at the opposite end, .

The asymmetric hklocking reactive mesogen compound represented by Formula 1a or 1b may be subjected to etherification, esterification using DCC catalyst, Pinnick-Lindgren oxidation, hydrolysis using 10% palladium-C catalyst , A nucleophilic acyl substitution reaction using SOCl ₂ , or the like.

Specifically, the asymmetric hklocking reactive mesogen compound represented by Formula 1a or 1b may be prepared as shown in Reaction Scheme 1 below. The following Reaction Scheme 1 is an example of the method for preparing the asymmetric hklocking reactive mesogen compound of the present invention, and the method of producing the asymmetric hklocking reactive mesogen compound of the present invention is not limited to the following Reaction Scheme 1.

[Reaction Scheme 1]

Referring to Reaction Scheme 1, the asymmetric hklocking reactive mesogen compound represented by Formula 1a or 1b of the present invention is a 4- (6- (acryloyloxy) hexyloxy) benzoic acid (4- (6- acryloyloxy) hexyloxy) benzoic acid and 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate ) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3- (2,4,6-Trifluorophenylcarboxy) 4,6-trifluorophenyl carboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate].

Hereinafter, a method for preparing an asymmetric hklocking reactive mesogen compound represented by formula (Ia) or (Ib) of the present invention will be described in detail.

(1) Synthesis of 4- (6- (acryloyloxy) hexyloxy) benzoic acid (4- (6- (acryloyloxy) hexyloxy) benzoic acid)

[Reaction Scheme 2]

The 4-hydroxybenzoic acid is dissolved in a solvent in the presence of KOH and KI using 4-hydroxybenzoic acid as a starting material, and then, 6-chloro- Is reacted with 6-chloro-1-hexanol to prepare 4- (6-hydroxyhexyloxy) benzoic acid (1). At this time, ethanol and distilled water may be mixed and used as the solvent.

Subsequently, the acid catalyst and the polymerization inhibitor are added to the 4-6 (hydroxyhexyloxy) benzoic acid (1) and acrylic acid to react in a solvent to obtain 4- (6- (acryloyloxy) hexyloxy) benzoic acid (2). The acid catalyst and polymerization inhibitor are not limited as long as they are commonly used in the art. Specifically, p-toluenesulfonic acid is used as the acid catalyst and hydroquinone is used as the polymerization inhibitor good. The solvent may be benzene.

(2) Synthesis of 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate

[Reaction Scheme 3]

Referring to Reaction Scheme 3, 3-hydroxybenzaldehyde is reacted with N, N'-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine , DMAP) and then reacted with 4- (benzyloxy) benzoic acid to obtain 3-formylphenyl 4- (benzyloxy) benzoate (3 ).

The prepared 3-formylphenyl 4- (benzyloxy) benzoate (3) and resorcinol were dissolved in a solvent, specifically, tetrahydrofuran, sodium chlorite and sodium chlorite were added to the mixed solution, A solution in which sodium phosphate monobasic monohydrate is dissolved is dropped and reacted to prepare 3-carboxyphenyl 4 (benzyloxy) benzoate (4).

The above-mentioned 3-carboxyphenyl 4- (benzyloxy) benzoate (4), 3,4,5- or 2,4,6-trifluorophenol (3,4,5- Or 2,4,6-, DCC and DMAP in a solvent to give 3,4,5- or 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate (3, 4,5- or 2,4,6-trifluorophenyl 3- [4- (benzyloxy] benzoate) (5). The solvent may be dichloromethane.

The above 3,4,5- or 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate (5) is dissolved in a solvent, specifically tetrahydrofuran, and 10% Pd C is added to the reaction mixture while hydrogen is being injected to form 3,4,5- or 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (3,4,5-or 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (6).

After dissolving the 3,4,5- or 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (6), DCC and DMAP in a solvent, 4- 4- (4- (benzyloxy) benzoyloxy) benzyloxy) benzoic acid to give 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (3,4,5-or 2,4,6-trifuorophenyl carboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate] (7).

Subsequently, the above 4- (4- (benzyloxy) benzoyloxy) benzoate (7) is dissolved in a solvent, specifically tetrahydrofuran The reaction was carried out by adding 10% Pd-C in the presence of hydrogen to give 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- [4-hydroxyphenyl] Benzoyloxy] benzoate (8).

(3) 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- {4- [6- (acryloyloxy) hexyloxy] benzoyloxy} benzoyloxybenzoate Synthesis of 3- (3,4,5-or 2,4,6-trifluorophenyl carboxy) phenyl 4- {4- [6- (acryloyloxy) hexyloxy] benzoyloxy} benzoyloxy benzoate

[Reaction Scheme 4]

(2) and 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) benzoic acid synthesized in the above reaction scheme 4, and the 4- (6- (acryloyloxy) ) Phenyl 4- (4-hydroxy) benzoyloxy] benzoate (8) is dissolved in a solvent, specifically dichloromethane anhydride, and reacted to obtain 3- (3,4,5-trifluorophenyl Carboxy) phenyl 4- {4- [6- (acryloyloxy) hexyloxy] benzoyloxy} benzoyloxybenzoate 3- (2,4,6-Trifluorophenylcarboxy) phenyl 4- {4- [6- (acryloyloxy) hexyloxy] benzoyloxy} benzoyloxybenzoate can be prepared.

The present invention also provides a liquid crystal composition comprising the compound represented by Formula 1a or 1b.

In the present invention, the compound represented by the above formula (1a) or (1b) and a vertical alignment material are mixed to form a liquid crystal composition for a vertical alignment mode A liquid crystal composition can be prepared.

The compound represented by Formula 1a or 1b is preferably included in the liquid crystal composition in an amount of 1 to 10% by weight, more preferably 1 to 5% by weight, and most preferably 2% by weight . When the content is less than 1% by weight, the effect may be insufficient. When the content is more than 10% by weight, the uniformity of the liquid crystal composition may be decreased.

The present invention also includes a liquid crystal orientation film prepared by coating the liquid crystal composition on a substrate followed by photo-curing, and a liquid crystal display device including the liquid crystal orientation film.

It is to be understood that the liquid crystal alignment film and the liquid crystal display device may be manufactured according to a known method used in the art, and these manufacturing methods do not limit the scope of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. These embodiments are for purposes of illustration only and are not intended to limit the scope of protection of the present invention.

The compounds synthesized in the following Examples were analyzed by FT-IR and ¹ H NMR to determine their synthesis.

Example 1. Synthesis of 4- (6- (acryloyloxy) hexyloxy) benzoic acid

1-1. Preparation of 4- (6-hydroxyhexyloxy) benzoic acid

First, 8.13 g (145 mmol) of potassium hydroxide and a small amount of potassium iodide were dissolved in a mixed solvent of 30 mL of ethanol and 20 mL of distilled water, and then 10.0 g (72.4 mmol) of 4-hydroxybenzoic acid was added and dissolved completely with stirring. Then 9.85 g (78.4 mmol) of 6-chloro-1-hexanol was slowly added dropwise over 10 minutes at room temperature while stirring rapidly, the temperature was raised to about 100 ° C, and the mixture was refluxed for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. The residue was dissolved in distilled water and washed three times with diethyl ether. A small amount of HCl was added until the pH of the aqueous layer became 2, and a white solid precipitated. After filtration, the precipitate was washed several times with distilled water and neutralized to pH 5. Finally, the precipitate was recrystallized from ethanol to give 4- (6-hydroxyhexyloxy) benzoic acid, a solid product in the form of a white powder.

Yield: 52%; ^{IR (KBr pellet, cm -1)} : 3338, 2949 (OH stretch), 1671 (. Conj C = O stretch), 1604, 1511 (Aromatic C = C stretch), 1422 (-CH 2 - CH bend), 1280 , 1172, 1059 (CO stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 8.00-7.95 (d, 2H, Ar-H), 7.04-6.99 (d, 2H, Ar-H), 4.13-4.05 (t, 2H _{, OCH 2), 3.58-3.51 (t} , 2H, OCH 2 (CH 2) 4 CH 2 OH), 1.85-1.74 (m, 2H, OCH 2 CH 2 (CH 2) 3 CH 2 OH), 1.58-1.47 _{(m, 6H, OCH 2 CH} 2 (CH 2) 3 CH 2 OH).

1-2. Preparation of 4- (6- (acryloyloxy) hexyloxy) benzoic acid

(58.8 mmol) of the obtained 4- (6-hydroxyhexyloxy) benzoic acid, 36.0 g (500 mmol) of acrylic acid, 2.00 g (11.7 mmol) of acid catalyst p-toluenesulfonic acid and 1.20 g of hydroquinone 11.8 mmol) was dissolved in benzene. The mixed solution was refluxed in a flask connected to a Dean stark trap for about 12 hours until the amount of stoichiometry produced through the reaction was removed. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in 300 mL of ethyl acetate. The mixed solution was washed with distilled water until no acrylic acid was found. At this time, the pH of the distilled water was checked to determine the presence of acrylic acid. Magnesium sulfate was added to the organic solution layer to dry the water. After filtration, the solvent was distilled off under reduced pressure and recrystallized from isopropyl alcohol to obtain 4- (6- (acryloyloxy) hexyloxy) benzoic acid as a white powdery solid .

Yield: 35.3%; ^{IR (KBr pellet, cm -1)} : 2941 (OH stretch), 1727 (. Conj C = O stretch), 1608 (Alkane C = C stretch), 1579, 1514 (Aromatic C = C stretch), 1430 (-CH ₂ -CH bend), 1261, 1255, 1171 (CO stretch); ^{1 H NMR (400 MHz, chloroform} -d 6, δ in ppm): 8.00-7.95 (d, 2H, Ar-H), 7.05-6.99 (d, 2H, Ar-H), 6.32-6.30, 5.90-5.88 _{(d, 2H, vinyl CH 2} = CH-), 6.17-14 (m, 1H, vinyl CH 2 = CH-), 4.42-4.35, 4.19-4.06 (m, 4H, OCH 2), 1.83-1.67 (m , 4H, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O), 1.65-1.49 (m, 4H, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O).

Example 2. 3- (3,4,5-Trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate Synthesis

2-1. Preparation of 3-formylphenyl 4- (benzyloxy) benzoate

(81.9 mmol) of 3-hydroxybenzaldehyde, 16.9 g (81.9 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP ) Was dissolved in 400 mL of dichloromethane, followed by stirring for 30 minutes. Then, 18.7 g (81.9 mmol) of 4- (benzyloxy) benzoic acid was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the urea was filtered out by filtration, and the remaining urea was removed by washing with distilled water three times. The solvent was distilled off under reduced pressure, and column chromatography was performed using a single solvent of dichloromethane as a developing solvent. Subsequently, the solvent was distilled off under reduced pressure, completely dissolved in a small amount of dichloromethane, and then methanol was added to precipitate to obtain 3-formylphenyl 4- (benzyloxy) benzoate as a white powdery solid.

Yield: 84.2%; IR (KBr pellet, cm ^-1 ): 3060 (Aromatic CH stretch), 2925, 2854, 2816 (Aliphatic CH stretch), 2741 (CH aldehyde), 1720 = C stretch), 1276, 1223, 1170 (CO stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 10.093 (s, 1H, Ar-CHO), 8.17 (d, J = 8 Hz, 2H, Ar-H), 7.88 (d, J = 1H, Ar-H), 7.82 (d, J = 4 Hz, 1H, Ar-H), 7.72 (t, J = 8 Hz, 1H, Ar-H), 7.638-7.630 H, Ar-H), 7.618-7.516 (m, 2H, Ar-H), 7.40 (t, J = 12 Hz, 3H, Ar- 5.29 (s, 2H, OCH3).

2-2. Preparation of 3-carboxyphenyl 4- (benzyloxy) benzoate

21.0 g (63.2 mmol) of the obtained 3-formylphenyl 4- (benzyloxy) benzoate and 6.95 g (63.2 mmol) of resorcinol were dissolved in 500 mL of tetrahydrofuran.

Separately, 46.3 g (379.1 mmol) of sodium chlorate and 39.1 g (190 mmol) of sodium phosphate monohydrate were completely dissolved in distilled water (250 mL), and a solution of 3-formylphenyl 4- (benzyloxy) It was slowly added dropwise over 10 minutes. As the dropwise addition progressed, the mixed solution gradually changed to yellow. The mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. After completion of the reaction, the volatile components were distilled off under reduced pressure, and the remaining materials were dissolved again in distilled water. Thereafter, the mixture was acidified by gradually adding HCl until the pH of the mixture became 2. As the acidification progressed, the color of the mixture gradually faded. The solid precipitate obtained after filtration was washed several times with distilled water and neutralized to pH 5. Filtered again and the precipitate was recrystallized from ethanol to give 3-carboxyphenyl 4- (benzyloxy) benzoate as a white solid.

Yield: 80.6%; ^{IR (KBr pellet, cm -1)} :( KBr pellet, cm-1): 3448-2345 (OH stretch), 3066 (Aromatic CH stretch), 2970, 2884, 2830 (Aliphatic CH stretch), 1720 (Conj C. = O stretch), 1610, 1513 (Aromatic C = C stretch), 1306, 1263, 1207, 1170 (CO stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 7.91 (t, J = 2 Hz, 2H, Ar-H), 7.61 (d, 1H, J = 8 Hz, Ar-H), 7.58 (s, 1H, Ar-H), 7.50-7.54 (m, 1H, Ar-H), 7.54-7.52 2H), 7.39 (t, J = 10 Hz, 1 H, Ar-H), 7.23-7.21 (m, 2H, Ar-H).

2-3. Preparation of 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate

(21.8 mmol) of the obtained 3-carboxyphenyl 4- (benzyloxy) benzoate, 4.97 g (21.8 mmol) of 3,4,5-trifluorophenol, 4.50 g (21.8 mmol) of DCC and 0.26 g (2.81 mmol) was dissolved in 100 mL of dichloromethane. The solution was stirred under nitrogen atmosphere at room temperature for 24 hours. After completion of the reaction, the urea was filtered out and washed with distilled water three times to remove the residual urea. The solvent was distilled off under reduced pressure, and column chromatography was performed using a single solvent of dichloromethane as a developing solvent. Subsequently, the solvent was distilled off under reduced pressure, completely dissolved in a small amount of dichloromethane, and methanol was added to precipitate to obtain 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] Benzoate. ≪ / RTI >

Yield: 89%; IR (KBr pellet, cm ^-1 ): 3067 (Aromatic C stretch), 2948, 2896 (Aliphatic CH stretch), 1727 (Conj. C = O stretch), 1605, 1530 , 1169 (CO, CF stretch); ¹ H NMR (400 MHz, CDCl ₃ ,? In ppm): 8.17-8.13 (m, 2H, Ar-H), 8.06-8.03 H), 7.56 (t, J = 8 Hz, 1H, Ar-H), 7.52-7.51 (m, 1H, Ar-H), 7.50-7.32 m, 2H, Ar-H), 6.95-6.90 (m, 2H, Ar-H), 5.18 (s, 2H, OCH3).

2-4. Preparation of 3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate

7.60 g (15.9 mmol) of the obtained 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in 200 mL of tetrahydrofuran. 0.35 g (3.26 mmol) of 10% Pd-C was added to the solution, and the mixture was stirred at 60 캜 for 12 hours while introducing hydrogen directly into the solvent. After completion of the reaction, the reaction mixture was filtrated, the solvent was distilled off under reduced pressure, the residue was completely dissolved in a small amount of tetrahydrofuran, and the residue was precipitated with an excess amount of hexane to obtain 3,4,5-trifluorophenyl 3 - [(4- Hydroxy) benzoyloxy] benzoate. ≪ / RTI >

Yield: 93.2%; IR (KBr pellet, cm ^-1 ): 3434 (OH stretch), 3077 (Aromatic CH stretch), 1738 (Conj. C = O stretch), 1607, 1525 (Aromatic C = C stretch), 1250, 1208, 1162 (CO, CF stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 8.15-8.00 (m, 4H, Ar-H), 7.73-7.64 (m, 2H, Ar-H), 7.39-7.41 (m, 2H , Ar-H), 7.04-7.01 (m, 2H, Ar-H).

2-5. Preparation of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate

7.60 g (19.6 mmol) of the obtained 3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate, 4.04 g (19.6 mmol) of DCC and 0.23 g (1.94 mmol) Was dissolved in 300 ml of dichloromethane, and the solution was stirred at room temperature for 30 minutes under a nitrogen atmosphere. Then, 4.47 g (19.6 mmol) of 4- (benzyloxy) benzoic acid was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the urea was filtered out and washed with distilled water three times to remove the residual urea. The solvent was distilled off under reduced pressure, and column chromatography was performed using a single solvent of dichloromethane as a developing solvent. Subsequently, the solvent was distilled off under reduced pressure, completely dissolved in a small amount of dichloromethane, and then methanol was added to precipitate to obtain 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- ( Benzyloxy) benzoyloxy] benzoate. ≪ / RTI >

Yield: 78%; IR (KBr pellet, cm ^-1 ): 3073 (Aromatic CH stretch), 2925, 2878 (Aliphatic CH stretch), 1725 (Conj. C = O stretch), 1607, 1522 , 1163 (CO, CF stretch) 1 H NMR (400 MHz, CDCl 3, δ in ppm): 8.29-8.25 (m, 2H, Ar-H), 8.17-8.14 (m, 2H, Ar-H), 8.08 H), 7.55-7.52 (m, 1H, Ar-H), 8.01 (t, J = (M, 2H, Ar-H), 5.16 (s, 1H, Ar-H), 7.45-7.34 _{2H, O-CH 2 -H)} .

2-6. Preparation of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate

8.00 g (13.4 mmol) of the obtained 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in 250 mL of tetrahydrofuran. 0.35 g (3.26 mmol) of 10% Pd-C was added to the solution, and the mixture was stirred at room temperature for 6 hours while introducing hydrogen directly into the solvent. After completion of the reaction, the reaction mixture was filtered, the solvent was distilled off under reduced pressure, and the residue was completely dissolved in a small amount of tetrahydrofuran, followed by the addition of an excess amount of hexane to precipitate 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate.

Yield: 88.4%; ^{IR (KBr pellet, cm -1)} : (KBr pellet, cm -1): 3073 (Aromatic CH stretch), 2925, 2878 (Aliphatic CH stretch), 1725 (. Conj C = O stretch), 1607, 1522 (Aromatic C = C stretch), 1275, 1252, 1163 (CO, CF stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 10.626 (s, 1H, OH), 8.25 (d, J = 8 Hz, 2H, Ar-H), 8.08-8.01 (m, 4H, Ar-H), 7.77-7.72 (m, 2H, Ar-H), 7.58-7.50 (m, 4H, Ar-H), 6.95 (d, J = 12 Hz, 2H, Ar-H).

Example 3 3- (3,4,5-Trifluorophenylcarboxy) phenyl 4- {4- [6- (acryloyloxy) hexyloxy] benzoyloxy} benzoyloxybenzoate

1.75 g (5.90 mmol) of 4- (6- (acryloyloxy) hexyloxy) benzoic acid (2) synthesized in Example 1 was flame-dried to completely remove water and dried ) Nitrogen flask and dissolved in 20 mL of thionyl chloride. While the solution was stirred at room temperature, 0.05 mL of pyridine was slowly added dropwise. The temperature was raised to 80 ° C and refluxed for 5 hours. After the completion of the reaction, the excess thionyl chloride was removed by distillation under reduced pressure, and 3- (3,4,5-trifluoroethoxy) benzoic acid was obtained in a molar ratio of 4- (6- (acryloyloxy) (5.90 mmol) of phenyl 4- [4-hydroxybenzoyloxy] benzoate (8) were dissolved in 50 ml of dichloromethane anhydride. To the mixed solution, 0.2 mL of pyridine was slowly added dropwise to dissolve it completely, and the mixture was allowed to react at room temperature for 48 hours. After completion of the reaction, the solvent was extracted with distilled water to remove pyridine. This material was dissolved in dichloromethane and purified by column chromatography using a single solvent of dichloromethane as a developing solvent. The solvent of the purified solution was distilled off under reduced pressure, and the resulting clear liquid material was cooled and dried to obtain a solid product of white crystals of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- {4- [6- Hexyloxy] benzoyloxy} benzoyloxybenzoate (formula 1a).

Yield: 50.3%; IR (KBr pellet, cm ^-1 ): 1601 (C = C Alkane), 1753, 1719 (conj. C = O stretch), 1473 (-CH ₂ -bend), 1199, 1169 (CF stretch), 1601, 1510 (C = C Aromatic), 2948 (CH Aromatic); ^{1 H NMR (400 MHz, CDCl} 3, δ in ppm): 8.31-8.26 (m, 4H, Ar-H), 8.15-8.01 (m, 4H, Ar-H), 7.55-7.52 (m, 2H, Ar -H), 7.41-7.37 (m, 4H , OCH 2), 6.99-6.92 (m, 4H, Ar-H), 6.41-6.36 (m, 1H, -CH = CH 2), 6.14-6.07 (m, _{1H, -CH = CH 2),} 5.82-5.79 (m, 1H, -CH = CH 2), 4.18-4.15 (m, 4H, O-CH 2).

Example 4. 3- (2,4,6-Trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate Synthesis

4-1. Preparation of 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate

(11.5 mmol) of 3-carboxyphenyl 4- (benzyloxy) benzoate obtained in Example 2, 2.62 g (11.5 mmol) of 2,4,6-trifluorophenol and 2.36 g (11.5 mmol) And 0.14 g (1.50 mmol) of DMAP were dissolved in 100 mL of dichloromethane. The solution was stirred under nitrogen atmosphere at room temperature for 24 hours. After completion of the reaction, the urea was filtered out and washed with distilled water three times to remove the residual urea. The solvent was distilled off under reduced pressure, and column chromatography was performed using a single solvent of dichloromethane as a developing solvent. Subsequently, the solvent was distilled off under reduced pressure, completely dissolved in a small amount of dichloromethane, and methanol was added to precipitate to obtain 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] Benzoate. ≪ / RTI >

Yield: 67.2%; IR (KBr pellet, cm ^-1 ): 3081 (Aromatic CH stretch), 2946, 2895 (Aliphatic CH stretch), 1728 (Conj. C = O stretch), 1604, 1518 , 1169 (CO, CF stretch); ¹ H NMR (400 MHz, CDCl ₃ ,? In ppm): 8.17-8.14 (m, 2H, Ar-H), 8.11-8.09 (M, 2H, Ar-H), 7.60-7.51 (m, 2H, Ar-H), 7.50-7.32 m, 2H, Ar-H) , 5.18 (s, 2H, O-CH 2 -H).

4-2. Preparation of 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate

7.45 g (9.41 mmol) of the obtained 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in 200 mL of tetrahydrofuran. 0.35 g (3.26 mmol) of 10% Pd-C was added to the solution, and the mixture was stirred at 60 캜 for 12 hours while introducing hydrogen directly into the solvent. After completion of the reaction, the reaction mixture was filtrated, the solvent was distilled off under reduced pressure, and the residue was completely dissolved in a small amount of tetrahydrofuran. The residue was precipitated by adding excess hexane to obtain 2,4,6-trifluorophenyl 3 - [(4- Hydroxy) benzoyloxy] benzoate. ≪ / RTI >

Yield: 68.2%; IR (KBr pellet, cm ^-1 ): 3534 (OH stretch), 3070 (Aromatic CH stretch), 1754 (Conj. C = O stretch), 1609, 1509 (Aromatic C = C stretch), 1289, 1258, 1212, 1165 (CO, CF stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 9.47 (S, 1H, OH), 8.16-8.08 (m, 4H, Ar-H), 7.77-7.70 (m, 2H, Ar-H ), 7.25-7.18 (m, 2H, Ar-H), 7.04-7.00 (m, 2H,

4-3. Preparation of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate

2.54 g (6.43 mmol) of the obtained 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate, 1.46 g (6.43 mmol) of DCC and 0.07 g Was dissolved in 200 ml of dichloromethane, and the solution was stirred at room temperature for 30 minutes under a nitrogen atmosphere. Then, 1.46 g (6.43 mmol) of 4- (benzyloxy) benzoic acid was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the urea was filtered out and washed with distilled water three times to remove the residual urea. The solvent was distilled off under reduced pressure, and column chromatography was performed using a single solvent of dichloromethane as a developing solvent. Subsequently, the solvent was distilled off under reduced pressure, completely dissolved in a small amount of dichloromethane, and methanol was added to precipitate to obtain 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- ( Benzyloxy) benzoyloxy] benzoate. ≪ / RTI >

Yield: 88.4%; IR (KBr pellet, cm ^-1 ): 3082 (Aromatic C stretch), 2956, 2927 (Aliphatic CH stretch), 1734 (Conj. C = O stretch), 1604, 1510 , 1163 (CO, CF stretch); ^{1 H NMR (400 MHz, CDCl} 3, δ in ppm): 8.29-8.26 (m, 2H, Ar-H), 8.16-8.11 (m, 3H, Ar-H), 8.06 (t, J = 2 Hz, 1H, Ar-H), 7.62-7.55 (m, 2H, Ar-H), 7.53-7.33 (m, 7H, Ar-H), 7.08-7.04 m, 2H, Ar-H) , 5.16 (s, 2H, O-CH 2 -H).

4-4. Preparation of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate

2.00 g (3.34 mmol) of the obtained 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in 100 mL of tetrahydrofuran. 0.35 g (3.26 mmol) of 10% Pd-C was added to the solution, and the mixture was stirred at room temperature for 6 hours while introducing hydrogen directly into the solvent. After completion of the reaction, the reaction mixture was filtrated, the solvent was distilled off under reduced pressure, the residue was completely dissolved in a small amount of tetrahydrofuran, and then an excess amount of hexane was added to precipitate to obtain 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate.

Yield: 71%; IR (KBr pellet, cm ^-1 ): 3534 (OH stretch), 3068 (Aromatic CH stretch), 1743 (Conj. C = O stretch), 1613, 1509 (Aromatic C = C stretch), 1255, 1219, CO, CF stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 10.6 (s, 1H, OH), 8.27-8.24 (m, 2H, Ar-H), 8.15-8.12 (m, 2H, Ar-H ), 8.03-8.01 (m, 2H, Ar-H), 7.83-7.81 (m, 2H, Ar-H), 7.79-7.51 -H).

Example 5 Synthesis of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- {4- [6- (acryloyloxy) hexyloxy] benzoyloxy} benzoyloxybenzoate

1.75 g (5.90 mmol) of 4- (6- (acryloyloxy) hexyloxy) benzoic acid (2) synthesized in Example 1 was flame-dried to completely remove water and dried ) Nitrogen flask and dissolved in 20 mL of thionyl chloride. While the solution was stirred at room temperature, 0.05 mL of pyridine was slowly added dropwise. The temperature was raised to 80 ° C and refluxed for 5 hours. After the completion of the reaction, the excess thionyl chloride was removed by distillation under reduced pressure to obtain 3- (2,4,6-trifluoro-benzoic acid) as a molar ratio of 4- (6- (acryloyloxy) (5.90 mmol) of phenyl 4- [4-hydroxybenzoyloxy] benzoate (8) were dissolved in 50 ml of dichloromethane anhydride. To the mixed solution, 0.2 mL of pyridine was slowly added dropwise to dissolve it completely, and the mixture was allowed to react at room temperature for 48 hours. After completion of the reaction, the solvent was extracted with distilled water to remove pyridine. This material was dissolved in dichloromethane and purified by column chromatography using a single solvent of dichloromethane as a developing solvent. The solvent of the purified solution was distilled off under reduced pressure, and the resulting clear liquid material was cooled and dried to obtain a solid product of white crystals, 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- {4- [6- Hexyloxy] benzoyloxy} benzoyloxybenzoate (formula (Ib)) was obtained.

Yield: 43.2%; IR (KBr pellet, cm ^-1 ): 1601 (C = C Alkane), 1753, 1719 (conj. C = O stretch), 1473 (-CH ₂ -bend), 1199, 1169 (CF stretch), 1601, 1510 (C = C Aromatic), 2948 (CH Aromatic); ^{1 H NMR (400 MHz, CDCl} 3, δ in ppm): 8.31-8.26 (m, 4H, Ar-H), 8.15-8.01 (m, 4H, Ar-H), 7.55-7.52 (m, 2H, Ar -H), 7.41-7.37 (m, 4H , OCH 2), 6.99-6.92 (m, 2H, Ar-H), 6.86-6.78 (m, 2H, Ar-H), 6.41-6.36 (m, 1H, _{-CH = CH 2), 6.14-6.07 (} m, 1H, -CH = CH 2), 5.82-5.79 (m, 1H, -CH = CH 2), 4.18-4.15 (t, 2H, O-CH 2) , 4.07-4.03 (t, 2H, O -CH 2).

Experimental Example 1. Identification of chemical structure

¹ H-NMR and FT-IR spectroscopy were used to determine the chemical structures of the compounds of formula (Ia) and (Ib) prepared in Examples 3 and 5 above.

The compound of formula (Ia) prepared in Example 3 is a compound in which the fluorine group is substituted at the 3,4,5-positions of the terminal. As shown in the IR spectrum shown in FIG. 1, the strong absorption band of the OH functional group attached to the carboxylic acid group appears in 2941㎝ ^-1, strong absorption band, unlike the compounds of the previous step shown in 3417㎝ ^-1 of OH functional groups attached to the phenol group, compounds of formula 1a prepared in example 3 is 2941㎝ ^-1, 3417㎝ ^-1 , the absorption band due to the stretching vibration of the aliphatic -CH at 3080 cm ^-1 , the absorption band due to the stretching vibration of C = O at 1739 cm ^-1 , and the absorption band at 1250, 1202, and 1158 , An absorption band due to stretching vibration of CO and CF appeared at 1058 cm ^-1 .

The results of ¹ H-NMR spectroscopy using acetone (Chloroform-d) substituted with deuterium as a solvent showed that the resonance peaks of protons in the phenyl group were 8.31 to 8.26 ppm, 8.15 to 8.01 ppm, 7.41 to 7.37 ppm, 6.99 ~ 6.92ppm, respectively. Hydrogen resonance of the fluorine - substituted phenyl group appeared at 7.55 ~ 7.52ppm. Hydrogen resonance of the double bond at the end of the flexible chain appeared at 6.41 ~ 5.79ppm, and the electron which attracted electrons decreased the density of electrons. Hydrogen resonance appeared at 4.18 ~ 4.15ppm, and hydrogen resonance of other alkyl carbon was found at 1.99 ~ 1.51ppm.

In addition, the compound of formula (Ib) prepared in Example 5 had a fluorine group-substituted compound at the 2,4,6-position of the terminal. As shown in the IR spectrum of FIG. 3, the strong absorption band of the OH functional group attached to the carboxylic acid group appears in 2941㎝ ^-1, a strong carbonyl absorption band the previous compound from those compounds of the formula 1b prepared in example 5 unlike shown in 3376㎝ ^-1 of OH functional groups attached to the acid group is 2941㎝ ^-1, 3376㎝ ^{- 1} , all the strong absorption bands of the OH functional groups disappeared. Also 3074㎝ in absorption band, 1732㎝ ^-1 due to the stretching vibration of an aliphatic -CH ^-1 due to the stretching vibration of C = O absorption band, and ^{1259㎝ -1, 1200㎝ -1, 1172㎝ -1} , 1065㎝ - ¹ , the absorption band due to stretching vibrations of CO and CF appeared. As a result of ¹ H-NMR spectrometry using acetone (Chloroform-d) substituted with deuterium as a solvent, the resonance peaks of the protons in the phenyl group were 8.31-8.26 ppm, 8.15-8.01 ppm, 7.41-7.37 ppm, 6.99-6.92ppm, and 6.86-6.78ppm, respectively. The hydrogen resonance of the fluorine - substituted phenyl group appeared at 7.55-7.52ppm. The hydrogen resonance in the double bond of the terminal short-chain in the flexible lattice appeared at 6.41-5.79ppm, and the carbon adjacent to the oxygen in the terminal alkyl chain The hydrogen resonance of the other alkyl carbons appeared at 1.86-1.43 ppm.

As described above, the compound represented by formula (1a) and the compound represented by formula (1b) prepared in Example 3 and Example 5, respectively, according to the present invention, were analyzed by IR spectroscopy and ¹ H- It was confirmed that the area ratio of the peak coincided with the expected value. In addition, elemental analysis of the compounds of formula (Ia) and (Ib) prepared in Examples 3 and 5 was carried out and is shown in Table 1 below.

As shown in Table 1, the abundance ratios of the compounds of formula (Ia) and compound (Ib) prepared in Examples 3 and 5 were compared with calculated values and measured values.

Experimental Example 2: Thermoelectric conversion behavior

The DSC thermograms of the compounds of formula (Ia) and (Ib) prepared in Examples 3 and 5 are shown in FIGS. 5 and 6, wherein the melting point transition temperature and meso phase transition The transition enthalpy and isotropy enthalpy between temperature and isotropic liquidus transition temperature, melting enthalpy and meso phase are shown in Tables 2 and 3 below. The DSC test was performed at a heating and cooling rate of 10 ° C / min under a nitrogen atmosphere. To minimize the thermal effect, the sample cooled after the first heating was measured by secondary heating.

As a result of the thermal analysis of the compound of formula (1a) prepared in Example 3, the compound of formula (Ia) showed two endothermic peaks at the time of the first heating in a temperature range in which thermal polymerization was impossible. The T _m was found at 116 ° C and the T _i at 138 ° C. During cooling, three exothermic peaks were observed. T _i was reversible at 136 ° C, transition between liquid crystals at 107 ° C, and crystallization at 60.5 ° C. In the second heating, T _m and T _i were 110.7 ° C and 138.5 ° C, respectively. Compounds of formula (I) in the temperature range where thermal polymerization is possible show T _m at 115 ° C and T _i at 138.4 ° C at the first heating. During cooling, T _i was observed at 183 ° C and transition between liquid crystals at 143 ° C. At 43 ° C, a large exotherm peak corresponding to crystallization appeared. During the second heating, solid - solid transition was observed at 68.2 ℃, T _m was at 87.9 ℃ and T _i was at 109.7 ℃.

As a result of the thermal analysis of the compound of Formula 1b prepared in Example 5, the compound of Formula 1b showed two endothermic peaks at the time of the first heating in a temperature range where thermal polymerization was not possible, as shown in FIG. The T _m was found at 107 ° C and the T _i at 125 ° C. Three exothermic peaks appeared during cooling. T _i reversibly appeared at 121 ° C, transition between liquid crystals at 114 ° C, and crystallization at 87.4 ° C. At the second heating, only T _m appeared at 120 ° C. The compound of formula (Ib) in the temperature range capable of thermal polymerization showed T _m at 107 ° C and T _i at 125 ° C during the first heating. During cooling, T _i was observed at 178 ° C and transition between liquid crystals at 158 ° C and 122 ° C. At the second heating, only T _m appeared at 120 ° C.

The above DSC results were in agreement with those obtained using a polarizing microscope.

Experimental Example 3. Polarizing Microscope Observation

Based on the transition temperature determined by DSC, the phase transition of the compounds of formula (Ia) and (Ib) prepared in Examples 3 and 5 above was observed under a polarizing microscope. The heating and cooling rates were measured at the same 10 ° C / min as in the DSC measurement conditions, and the observed optical structures of each compound are shown in FIGS. 7 to 10. The results obtained using a polarization microscope were able to observe the phase transition temperature consistent with the phase transition temperature obtained by DSC analysis.

7 and 8 is a compound of formula (1a) compound 10 was heated to the isotropic region to the ^o C / hour cooling at a rate of min 130 ^o formula into an optical picture observed in C 1a prepared in Example 3 is a smectic phase .

FIGS. 9 and 10 are optical photographs of the compound of Formula 1b prepared in Example 5, showing a focal conic phase in a smectic phase at 120 ^° C during heating and cooling. Also, as shown in FIG. 10, the compound of formula (1b) was found to be a monolithic liquid crystal exhibiting a liquid crystal phase only upon cooling.

On the other hand, upon heating at a high temperature at which the temperature could be thermally polymerized, the compound of formula (Ia) exhibited a broad liquid crystal phase at 182 ^° C and the compound of formula (Ib) ranged from 178 ^° C. Is a monolithic liquid crystal showing a liquid crystal phase only at the time of cooling.

Example 6. Composite cell manufacturing

In order to fabricate a composite system specimen, AL60702 of JSR Corporation, which has vertical orientation properties, was used as an alignment agent. The liquid crystal was MLC-6608 (Δn: 0.083, Δε: -4.1, Tni: 90 ° C.) of a negative dielectric constant anisotropy Respectively. Prior to the cell preparation, the compound of formula (1a) prepared in Example 3 and the compound of 1b prepared in Example 5 were mixed with (2% by weight) vertical aligning agent and stirred for 24 hours, Production process.

For the cell preparation, the ITO substrate was first cut into an appropriate size (2 cm ㅧ 2.5 c) and cleaned thoroughly. Thereafter, the compound of Formula 1a or the compound of Formula 1b (2 wt% each) The mixture was spun onto an ITO substrate and spin coated. The coating conditions were controlled at 1,000 rpm for 10 seconds and at 3,000 rpm for 20 seconds at 2 steps. The spin rpm and aceelation of the spin coater were adjusted to control the coating thickness. After spin-coating, the solution was pre-baked at 100 ° C for 10 minutes to remove the solvent, and hard-baked at 180 ° C for 1 hour to be imidized. Then, a cell was fabricated by using a photo-curing agent and a spacer corresponding to a cell gap to be fabricated. The fabricated cell had a thickness of 3.3 탆. After completion of the cell fabrication, Merck's nematic liquid crystal, MLC-6608 (Δn: 0.083, Δε: -4.1, Tni: 90 ° C.) was injected at a clearing point of 90 ° C. Thereafter, a voltage of 10 V was applied at room temperature, and ultraviolet light of 365 nm wavelength was irradiated for 30 minutes to be photocured.

Experimental Example 4: Solubility evaluation

In order to be applied to the VA mode, the coating properties of the vertical alignment layer in which the compound of Formula 1a or the compound of Formula 1b are mixed should be uniformly maintained. The solubility of the compound of formula (Ia) or the compound of formula (Ib) should be determined, and in this example, the solubility of the compound of the present invention to the PI which is the orienting agent was confirmed, Respectively.

PI + Compounds of the present invention Solubility AL60702 + RM257 (2.0% by weight)

AL60702 + Compound of formula (1a) (2.0% by weight)

AL60702 + Compound of formula 1b (2.0% by weight)

As shown in Table 4, the solubility of the PI as the aligning agent and the compound of the formula (1a) or the compound of the formula (1b) was visually identifiable together with the RM257 of Merck, which is the comparative object, and the solubility of the PI I could.

EXPERIMENTAL EXAMPLE 5. Evaluation of Coating Property

In order to confirm the coating properties after mixing the compound of Formula 1a or the compound of Formula 1b with the vertical alignment layer of commercially available RM257 of Merck Co., photopolymerization was performed by irradiating ultraviolet rays, and the surface characteristics were observed. . At this time, the content of the compound of formula (1a) or the compound of formula (1b) and the commercialized RM257 of Merck were both fixed to 2% by weight with respect to the vertical alignment agent, and the surface characteristics of each cell were confirmed after the above-mentioned process steps.

As shown in Fig. 11, the black state of the compound (b) of Formula 1a and the compound (c) of Formula 1b showed a black state that was indistinguishable as in the black state RM257 of Merck Co., , It was confirmed that the compound of formula (Ia) or (Ib) of the present invention does not give an optical defect to such a degree that light leakage phenomenon occurs, and thus, it is suitable for VA mode.

Experimental Example 6: Electrical / Optical Properties

Nematic liquid crystal (MLC-6608 (? N: 0.083, ??: -4.1, Tni: 90 占 폚) was injected into the cell prepared in Example 6, and a voltage of 10 V was applied at room temperature. Ultraviolet rays of 365 nm And the photocuring was carried out for 30 minutes by irradiating with ultraviolet light, and when the photocuring was performed by irradiating ultraviolet light, and when the photocuring was not performed, the optical tissue change of the aligned liquid crystal was observed by turning on / Respectively.

As shown in Table 5, in the case of not irradiating ultraviolet rays, optical tissues in the alignment film containing RM-257 and the compound of formula (I) or (Ib) were changed every time the voltage was turned on / off. The time taken to stabilize was 50 s, 49 s, and 56 s, respectively.

On the other hand, in the case of the photocured thin film irradiated with ultraviolet rays, it was found that the same optical structure appeared every time the voltage was turned on / off. The time required for stabilization of the optical structure was found to be 10 ms, 1.1 s, and 800 ms, respectively. It was judged that the compound represented by formula (1a) and the compound represented by formula (1b) .

Although the present invention has been described in terms of the preferred embodiments mentioned above, it is possible to make various modifications and variations without departing from the spirit and scope of the invention. It is also to be understood that the appended claims are intended to cover such modifications and changes as fall within the scope of the invention.

Claims (12)

An asymmetric hklocking reactive mesogen compound represented by the following formula (1) having a benzene number of 5 (5-ring) and having a fluorine substituent at benzene at one end:
[Chemical Formula 1]

In Formula 1,
R is

or

ego,
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least three of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are F,
Z is -COO, -C = O, -CN = N or -NN,
m is an integer of 0 to 1,
n is an integer from 3 to 5,
y is an integer from 3 to 12; The method according to claim 1,
Wherein the asymmetric hklocking reactive mesogen compound is a compound represented by the following formula (1a) or (1b):
[Formula 1a]

[Chemical Formula 1b]

(4- (6- (acryloyloxy) hexyloxy) benzoic acid and 4- (3,4,5-trifluorophenylcarboxy) phenyl 4- [ Which comprises reacting 4- (4-hydroxybenzoyloxy) benzoate of formula (I), which comprises reacting 4- (hydroxy) benzoyloxybenzoate Method of producing asymmetric hocky stick type reactive mesogen compound:
[Formula 1a]

(4- (6- (acryloyloxy) hexyloxy) benzoic acid and 3- (2,4,6-trifluorophenylcarboxy) phenyl 4 [4 - (hydroxy) benzoyloxy] benzoate represented by the following formula (1b), which comprises reacting 3- (2,4,6-trifluorophenyl carboxy) phenyl 4- [ Method of producing a hockey stick type reactive mesogen compound:
[Chemical Formula 1b]

The method according to claim 3 or 4,
The 4- (6- (acryloyloxy) hexyloxy) benzoic acid is,
4-hydroxybenzoic acid and 6-chloro-1-hexanol were reacted to prepare 4- (6-hydroxyhexyloxy) benzoic acid (4- (6- hydroxyhexyloxy) benzoic acid; And
Reacting the 4- (6-hydroxyhexyloxy) benzoic acid with acrylic acid to prepare 4- (6- (acryloyloxy) hexyloxy) benzoic acid;
≪ RTI ID = 0.0 > 1, < / RTI > The method of claim 3,
The 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy]
(SA1) 3-hydroxybenzaldehyde and 4- (benzyloxy) benzoic acid to obtain 3-formylphenyl 4- (benzyloxy) benzoate - (benzyloxy) benzoate);
(SA2) The above-mentioned 3-formylphenyl 4- (benzyloxy) benzoate, resorcinol, sodium chlorite and sodium phosphate monobasic monohydrate are reacted to prepare 3-carboxyphenyl To produce 4- (benzyloxy) benzoate (3-carboxyphenyl 4 (benzyloxy) benzoate);
(SA3) The above 3-carboxyphenyl 4- (benzyloxy) benzoate and 3,4,5-trifluorophenol were reacted to prepare 3,4,5-trifluorophenyl 3 - [4- (benzyloxy) benzoyloxy] benzoate (3,4,5-trifluorophenyl 3- [4- (benzyloxy] benzoate);
(SA4) Reaction of 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate, Pd-C and hydrogen to give 3,4,5-trifluorophenyl 3- [ (4-hydroxy) benzoyloxy] benzoate (3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate;
(SA5) By reacting the above 3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate and 4- (benzyloxy) benzoic acid, 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate 3- (3,4,5-trifuorophenyl carboxy) phenyl 4- [4- benzoyloxy] benzoate; and
(SA6) A process for producing 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate, Pd- 5-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate;
≪ RTI ID = 0.0 > 1, < / RTI > 5. The method of claim 4,
The above-mentioned 3- (2,4,6-trifluorophenylcarboxy) phenyl 4 [4- (hydroxy) benzoyloxy]
(SB1) 3-hydroxybenzaldehyde and 4- (benzyloxy) benzoic acid to obtain 3-formylphenyl 4- (benzyloxy) benzoate - (benzyloxy) benzoate);
(SB2) The above-mentioned 3-formylphenyl 4- (benzyloxy) benzoate, resorcinol, sodium chlorite and sodium phosphate monobasic monohydrate were reacted to prepare 3-carboxyphenyl To produce 4- (benzyloxy) benzoate (3-carboxyphenyl 4 (benzyloxy) benzoate);
(SB3) The above 3-carboxyphenyl 4- (benzyloxy) benzoate and 2,4,6-trifluorophenol were reacted to prepare 2,4,6-trifluorophenyl 3 - [4- (benzyloxy) benzoyloxy] benzoate (2,4,6-trifluorophenyl 3- [4- (benzyloxy] benzoate);
(SB4) By reacting 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate, Pd-C and hydrogen, 2,4,6-trifluorophenyl 3- [ (4-hydroxy) benzoyloxy] benzoate (2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate;
(SB5) By reacting the above 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate and 4- (benzyloxy) benzoic acid, 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate 3- (2,4,6-Trifluorophenylcarboxy) phenyl 4- [4- benzoyloxy] benzoate; and
(SB6) reacting the 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate, Pd- 6-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate;
≪ RTI ID = 0.0 > 1, < / RTI > Claims [1] A liquid crystal composition comprising an asymmetric hklocking reactive mesogen compound represented by the following formula
[Chemical Formula 1]

In Formula 1,
R is

or

ego,
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least three of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are F,
Z is -COO, -C = O, -CN = N or -NN,
m is an integer of 0 to 1,
n is an integer from 3 to 5,
y is an integer from 3 to 12; 9. The method of claim 8,
Wherein the asymmetric hklocking reactive mesogen compound is a compound represented by the following formula (1a) or (1b):
[Formula 1a]

[Chemical Formula 1b]

9. The method of claim 8,
The liquid crystal composition according to claim 1, wherein the asymmetric hklocking reactive mesogen compound represented by Formula 1 is contained in the liquid crystal composition in an amount of 1 to 10 wt%. A liquid crystal orientation film, characterized in that the liquid crystal alignment film is produced by coating the liquid crystal composition described in claim 8 on a substrate and then photocuring. A liquid crystal display device comprising the liquid crystal orientation film according to claim 11.

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