KR101641705B1 - Polymerizable liquid crystal compounds, liquid crystal composition comprising the compounds, and optical film comprising the composition - Google Patents

Abstract

The present invention relates to a polymerizable liquid crystal compound, a liquid crystal composition containing the same, and an optical film. The polymerizable liquid crystal compound according to the present invention has at least two substituents capable of intermolecular bonding in the molecule, and it is possible to form a liquid crystal layer having high orientation stability upon coating a composition containing the same. Accordingly, the optical film formed using the composition can be suitably used for a liquid crystal display or an antireflection film for an OLED type display.

Description

POLYMERIZABLE LIQUID CRYSTAL COMPOUNDS, LIQUID CRYSTAL COMPOSITION COMPRISING THE COMPOUNDS, AND OPTICAL FILM COMPRISING THE COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable liquid crystal compound,

The present invention relates to a polymerizable liquid crystal compound, a liquid crystal composition containing the same, and an optical film.

As the market share of LCD (liquid crystal display) rises in the display field, interest in organic light emitting diodes (OLED), which is considered as the next generation display, is gradually increasing.

OLED displays are superior to LCDs in terms of thickness, power consumption, response speed, and viewing angle, and can be applied to various applications such as transparent products and flexible products.

However, the OLED has a short life span and a low luminous efficiency, so that the OLED is still limited in its size. In particular, it is difficult to realize a perfect black color due to interference of external light.

For a more complete black implementation, a method has been proposed that uses two polarizing films on an OLED display to minimize interference from external light. Although the method of using two polarizing films is relatively simple, it affects the sharpness of the display and raises the manufacturing cost.

Accordingly, various methods for minimizing interference due to external light, such as a method using a reverse wavelength dispersive liquid crystal film instead of the polarizing film, have been proposed, but the effect is still insufficient.

The present invention is intended to provide a polymerizable liquid crystal compound which can be suitably used in an anti-radiation film or the like by allowing formation of a liquid crystal layer having high orientation stability.

The present invention also provides a polymerizable liquid crystal composition comprising the compound and an optical film.

According to the present invention, there is provided a polymerizable liquid crystal compound represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

A is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkynylene group having 2 to 6 carbon atoms;

L ₁ , L ₂ , and L ₃ are each independently a single bond or a divalent linking group, and at least one of L ₁ , L ₂ , and L ₃ is a divalent linking group;

E ₁ and E ₂ are each independently a substituted or unsubstituted aromatic group or heteroaromatic group having 6 to 20 carbon atoms;

D ₁ is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms;

D ₂ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms;

R ₁ and R ₂ are each independently a cycloalkylene group having 3 to 12 carbon atoms;

G is a hydroxy group or an amine group.

J is a single substituent selected from the group consisting of the following formula (2);

(2)

n is an integer of 1 to 10;

According to the present invention, E ₁ and E ₂ may each independently be a benzene ring, a naphthalene ring, or a phenanthrene ring.

Further, according to the present invention, each of R ₁ and R ₂ may independently be a cyclohexane ring or a cyclohexene ring.

According to the present invention, the divalent linking group in L ₁ , L ₂ , and L ₃ in Formula 1 is -O-, -S-, -CO-, -CO-O-, -O- O-, -CO-NR-, -NR-CO-, -NR-CO-NR-, -O (CH ₂ ) _x -, - (CH ₂ ) _x O-, -CH = CHCH _{2 O-, -OCH 2 CH = CH-,} - (CH 2) x COO-, -OCO (CH 2) x -, - (CH 2) x OCO-O-, -OCO-O- (CH 2) x _{-, -SCH 2 -, -CH 2} S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, - (CH 2) x -, -CF 2 CH 2 - , -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH═CH-, -C≡C-, -CH═N-, -N═CH-, or -N═N-. Here, each R is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and each x may independently be an integer of 1 to 8.

On the other hand, according to the present invention, there is provided a polymerizable liquid crystal composition and an optical film comprising the compound represented by the formula (1).

The polymerizable liquid crystal compound according to the present invention includes at least two substituents capable of intermolecular bonding in the molecule, and it is possible to form a liquid crystal layer having high orientation stability upon coating a composition containing the same. In particular, when an optical film produced using the above composition is applied to an OLED type display, interference due to external light can be minimized, thereby achieving a more perfect black color.

Hereinafter, a polymerizable liquid crystal compound according to embodiments of the present invention and a liquid crystal composition containing the same will be described.

Prior to that, unless explicitly stated throughout the present specification, the terminology is for reference only, and is not intended to limit the invention.

And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning.

Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.

&Quot; Polymerizable liquid crystal compound " means a liquid crystal compound having at least one polymerizable functional group. When a composition containing the polymerizable liquid crystal compound is oriented in a liquid crystal state and an active energy ray such as ultraviolet light is irradiated in that state, a polymerized substance in which the alignment structure of the liquid crystal molecules is immobilized can be obtained. The polymer thus obtained is anisotropic in physical properties such as refractive index, permittivity, magnetic susceptibility, elastic modulus and thermal expansion coefficient, and thus can be applied as an optical anisotropic material such as a retardation plate, a polarizing plate, a polarizing prism, a brightness enhancement film, Do.

Meanwhile, the inventors of the present invention have confirmed that the polymerizable liquid crystal compound having the structure represented by the following formula (1) enables formation of a liquid crystal layer having higher orientation stability in the course of research on polymerizable liquid crystal compounds. The optical film formed using the polymerizable liquid crystal compound can be suitably used for a liquid crystal display or an antireflection film for an OLED type display, and is applicable to an OLED type display to enable a more complete black display. Respectively.

According to one embodiment of the present invention, there is provided a polymerizable liquid crystal compound represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

A is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkynylene group having 2 to 6 carbon atoms;

L ₁ , L ₂ , and L ₃ are each independently a single bond or a divalent linking group, and at least one of L ₁ , L ₂ , and L ₃ is a divalent linking group;

E ₁ and E ₂ are each independently a substituted or unsubstituted aromatic group or heteroaromatic group having 6 to 20 carbon atoms;

D ₁ is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms;

D ₂ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms;

R ₁ and R ₂ are each independently a cycloalkylene group having 3 to 12 carbon atoms;

G is a hydroxy group or an amine group.

J is a single substituent selected from the group consisting of the following formula (2);

(2)

n is an integer of 1 to 10;

The polymerizable liquid crystal compound represented by the formula (1) has a structure in which at least two substituents capable of intermolecular bonding are introduced into a molecule, and a liquid crystal layer having a higher orientation stability . ≪ / RTI > In one embodiment, the substituent capable of intermolecular bonding can be introduced into G and L ₁ , L ₂ , and L ₃ of Formula 1.

In one embodiment, A in the formula (1) is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkynylene group having 2 to 6 carbon atoms. Here, the alkylene, alkenylene or alkynylene group may be linear or branched. At least one hydrogen contained in the alkylene, alkenylene or alkynylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group. Wherein said substitution can be a single substitution or a multiple substitution of two or more. Also, at least one -CH ₂ - group constituting the alkylene group, alkenylene group or alkynylene group may be substituted with -S- or -O-.

In one embodiment, each of L ₁ , L ₂ , and L ₃ in Formula 1 may independently be a single bond or a divalent linking group. Wherein the divalent linking group is selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, , -NR-CO-NR-, -O (CH ₂ ) _x -, - (CH ₂ ) _x O-, -CH═CHCH ₂ O-, -OCH ₂ CH═CH-, - (CH ₂ ) _x COO _{-, -OCO (CH 2) x} -, - (CH 2) x OCO-O-, -OCO-O- (CH 2) x -, -SCH 2 -, -CH 2 S-, -CF 2 O _{-, -OCF 2 -, -CF 2} S-, -SCF 2 -, - (CH 2) x -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CH = - CH = -, -C = C-, -CH = N-, -N = CH-, or -N = N-; Each R is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and x may independently be an integer of 1 to 8.

In one embodiment, each of E ₁ and E ₂ in Formula 1 is independently a substituted or unsubstituted aromatic group or heteroaromatic group having 6 to 20 carbon atoms. Here, the heteroaromatic group may be an aromatic group in which one or more CH groups are substituted by N, or one or two non-adjacent CH ₂ groups may be substituted by O, S, or O and S.

In particular, in E ₁ and E ₂ of the above formula (1), at least one hydrogen contained in the aromatic group and the heteroaromatic group may be substituted into a group enabling an intermolecular bond of the polymerizable liquid crystal compound . According to one embodiment, at least one hydrogen contained in the aromatic group and the heteroaromatic group is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, An alkynyl group having 2 to 6 carbon atoms, an alcohol group having 1 to 5 carbon atoms, an amine group, a carboxy group, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.

According to one embodiment, E ₁ and E ₂ in Formula 1 may be a benzene ring, a naphthalene ring, or a phenanthrene ring, and at least one hydrogen contained in the ring may be substituted with the above-described functional group.

In one embodiment, D ₁ in Formula ₁ is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms. Here, the alkylene group may be linear or branched. The at least one hydrogen contained in the alkylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group. Wherein said substitution can be a single substitution or a multiple substitution of two or more. Also, at least one -CH ₂ - group constituting the alkylene group may be substituted with -S- or -O-.

In one embodiment, D ₂ in Formula 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Here, the alkyl group may be linear or branched. The at least one hydrogen contained in the alkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group. Wherein said substitution can be a single substitution or a multiple substitution of two or more. In addition, at least one -CH ₂ - group constituting the alkyl group may be substituted with -S- or -O-.

In one embodiment, each of R ₁ and R ₂ in Formula 1 is independently a cycloalkylene group having 3 to 12 carbon atoms. Particularly, at least one hydrogen contained in the cycloalkylene group is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alcohol group, an amine group, a carboxyl group, a halogen atom, An alkoxy group having 1 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms. According to one embodiment, each of R ₁ and R ₂ in Formula 1 may be independently a cyclohexane ring or a cyclohexene ring, and at least one hydrogen contained in the ring may be substituted with the above-mentioned functional group.

In one embodiment, G in Formula 1 is a hydroxyl group or an amine group.

In one embodiment, J in Formula 1 is a substituent selected from the group consisting of Formula 2 below.

(2)

&Quot; * "in the above formula (2) represents a moiety bonded to the substituent D ₁ in the above formula (1).

In one embodiment, n in the formula ( ₁ ) is an integer of 1 to 10, preferably 2 to 8, as a repeating unit of - (D ₁ ) -.

The polymerizable liquid crystal compound of Formula 1 may be, for example, a compound represented by Formula 3 below. However, the polymerizable liquid crystal compound according to one embodiment is not limited to the compound of the following formula (3).

(3)

Here, m may be 4 to 8.

The polymerizable liquid crystal compound represented by the above formula (1) can be synthesized by applying known reactions, and a more detailed synthesis method will be described in detail in the examples.

According to another embodiment of the present invention, there is provided a polymerizable liquid crystal composition comprising the compound represented by Formula 1.

The polymerizable liquid crystal composition according to one embodiment may be a composition obtained by dissolving the compound represented by Formula 1 together with a polymerization initiator in a solvent. The compound represented by Formula 1 may be included in the composition alone or in combination of two or more.

As the polymerization initiator, a radical polymerization initiator that is conventional in the art may be used. The content of the polymerization initiator can be determined within a conventional range that can efficiently lead to the polymerization reaction of the polymerizable liquid crystal compound. As a non-limiting example, the polymerization initiator may be included in an amount of 10% by weight or less, preferably 0.5 to 8% by weight based on the total weight of the composition.

The solvent may be selected from the group consisting of benzene, toluene, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethylether , Diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene Methylene-2-pyrrolidone, dimethylformamide, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachlorethylene, tetrahydrofuran, Chlorobenzene, t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, Butyl cellosolve, in tilsel may be a cellosolve, or a mixture thereof. Among these solvents, those having a boiling point of 60 to 250 占 폚 are advantageous in forming a uniform film thickness upon application of the composition, and are advantageous in minimizing the deterioration of the residual solvent and the orientation of the solvent.

The polymerizable liquid crystal composition may further contain a sensitizer such as xanthone, thioxanthone, chlorothioxanthone, phenothiazine, anthracene and diphenylanthracene, if necessary.

The polymerizable liquid crystal composition may further contain, if necessary, a quaternary ammonium salt, an alkylamine oxide, a polyamine derivative, a polyoxyethylene-polyoxypropylene condensate, sodium laurylsulfate, ammonium laurylsulfate, an alkyl substituted aromatic sulfonic acid salt, Surfactants such as phosphates and perfluoroalkylsulfonates; Storage stabilizers such as hydroquinone, hydroquinone monoalkyl ethers, pyrogallol, thiophenols, 2-naphthyl amines and 2-hydroxynaphthalenes; Antioxidants such as 2,6-di-t-butyl-p-cresol and triphenylphosphite; An ultraviolet absorber such as a salicylate ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, or a nickel complex salt compound may be further included.

In addition, the polymerizable liquid crystal composition may further include fine particle-like materials for adjusting the optical anisotropy or improving the strength of the polymer film, if necessary. The particulate cargo hectorite, montmorillonite, _{kaolinite, ZnO, TiO 2, CeO 2} , Al 2 O 3, Fe 2 O 3, ZrO 2, MgF 2, SiO 2, SrCO 3, Ba (OH) 2, Ca (OH ) ₂ , Ga (OH) ₃ , Al (OH) ₃ , Mg (OH) ₂ and Zr (OH) ₄ ; Carbon nanotubes, fullerene, dendrimer, polyvinyl alcohol, polymethacrylate, polyimide, and the like.

In addition, the polymerizable liquid crystal composition may further contain an optional liquid crystal compound in addition to the compound represented by the formula (1), and the optional liquid crystal compound may or may not have a polymerizable property. Examples of the optional liquid crystal compound include a liquid crystal compound having an ethylenic unsaturated bond, a compound having an optically active group, and a rod-like liquid crystal compound. The optional liquid crystal compounds may be mixed in an appropriate amount depending on their structure. Preferably, the compound represented by Formula 1 is contained in an amount of 20 wt% or more, or 50 wt% or more of the total weight of the liquid crystal compound May be advantageous in terms of achieving the above-mentioned object.

According to another embodiment of the present invention, there is provided an optical film formed using the polymerizable liquid crystal composition.

In particular, the optical film according to one embodiment may include a liquid crystal layer which can exhibit a regular wavelength dispersion and has a high orientation stability as the optical film contains the above-mentioned polymerizable liquid crystal compound.

The optical film according to the embodiment is obtained by applying the polymerizable liquid crystal composition described above to a support substrate, desolvating the liquid crystal compound in the polymerizable liquid crystal composition in an aligned state, and then irradiating with an energy ray to obtain .

Here, the supporting substrate is not particularly limited, but preferred examples thereof include a glass plate, a polyethylene terephthalate film, a polyimide film, a polyamide film, a polymethyl methacrylate film, a polystyrene film, a polyvinyl chloride film, a polytetrafluoroethylene film , A cellulose-based film, a silicon film, or the like can be used. A polyimide alignment film or a polyvinyl alcohol alignment film may be preferably used on the supporting substrate.

For example, a roll coating method, a spin coating method, a bar coating method, a dip coating method, a spray coating method, or the like can be applied as a method of applying the composition to the support substrate. The thickness of the film formed by the composition may vary depending on the application, and may be selected in the range of preferably 0.01 to 100 탆.

On the other hand, as a non-limiting example of the method of orienting the liquid crystal compound, a method of performing a pre-alignment treatment on a support substrate can be mentioned. Examples of the method of performing the alignment treatment include a method of forming a liquid crystal alignment side including various polyimide alignment films or a polyvinyl alcohol alignment film on a support substrate and then performing a treatment such as rubbing. Further, a method of applying a magnetic field or an electric field to the composition on the support substrate and the like can be mentioned.

The method of polymerizing the polymerizable liquid crystal composition may be a known method using light, heat or electromagnetic waves.

The optical film may be used as a retardation film, a polarizing element, an antireflection film, an electrospinning film, a viewing angle compensating film, etc. of a liquid crystal display or an OLED type display. In particular, when an optical film formed using the above composition is applied to an OLED-type display, interference due to external light can be minimized, thereby achieving a more perfect black color.

In particular, the value of the retardation R ₅₅₀ at a wavelength of 550 nm with respect to the optical film may be 120 to 150 nm, preferably 123 to 145 nm. The ratio (R ₄₅₀ / R ₅₅₀ ) of the retardation R ₄₅₀ at a wavelength of 450 nm to the retardation R ₅₅₀ at a wavelength of 550 nm may be 1.05 or less, or 0.5 to 1.05, preferably 0.99 or less. The optical film exhibits such a retardation value, exhibits reverse dispersion (or flat dispersion), and is excellent in orientation stability. When applied to an OLED type display, interference due to external light can be minimized, thereby achieving a more perfect black color .

Hereinafter, the functions and effects of the present invention will be described in more detail with reference to specific embodiments of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

Example 1: Synthesis of compound RM-01

[Chemical Formula 4]

 The compound RM-01 of the formula 4 was synthesized according to the reaction mechanism as shown in the following reaction scheme 1.

[Reaction Scheme 1]

(Synthesis of Compound 2)

27 mL of ethynyltrimethylsilane and 22 g of tetramethylenediamine were dissolved in tetrahydrofuran and 83.2 mL of n-butyl lithium was added thereto under a nitrogen atmosphere at -78 ° C. . After stirring for about 1 hour, the compound 1, 4'-pentyldicyclohexylanone ((4'r) -4'-pentyl- [1,1'-bi (cyclohexan)] - 4 -one) was added dropwise thereto, followed by stirring at 78 ° C for 2 hours. The reaction solution was warmed to room temperature, distilled water was added thereto, and the mixture was extracted with ethyl acetate. The organic layer was chemically dried and then the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 41.23 g of Compound 2. [

(Synthesis of Compound 3)

About 21.91 g of Compound 2 and about 26.04 g of potassium carbonate (K ₂ CO ₃ , potassium carbonate) were dissolved in tetrahydrofuran and stirred at room temperature for one day. Then, distilled water was added dropwise to the reaction solution, extracted with ethyl acetate, the organic layer was chemically dried, and the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 14.03 g of Compound 3. [

(Synthesis of Compound 4)

About 7.25 g of Compound 3 and about 7.25 g of 4- (methoxymethoxy) benzoic acid, about 20.82 g of 4- (dimethylamino) pyridine) , About 13.33 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) was dissolved in dichloromethane and stirred at 40 占 폚 for one day. The reaction solution was diluted with dichloromethane, washed with distilled water and brine, and chemically dried. Thereafter, the product was obtained by filtration and vacuum distillation, which was purified by column chromatography to obtain about 8.37 g of Compound 4. [

(Synthesis of Compound 5)

About 8.3 g of Compound 4 was dissolved in tetrahydrofuran, and a 6 N hydrochloric acid solution was added dropwise thereto, followed by stirring at room temperature for one day. Then, distilled water was added dropwise to the reaction solution, extracted with ethyl acetate, the organic layer was chemically dried, and the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 7.5 g of Compound 5. < 1 >

(Synthesis of Compound 6-1)

About 3.05 g of compound 5 and about 2.53 g of (lr, 4r) -4 - ((4- (acryloyloxy) butoxy) carbonyl) cyclohexanecarboxylic acid [ (N, N-diisopropylethylamine) and about 2.95 g of EDC were dissolved in dichloromethane and the resulting mixture was stirred at room temperature for 1 hour. Followed by stirring at 40 ° C for one day. The reaction solution was diluted with dichloromethane, washed with distilled water and brine, and chemically dried. Filtration and vacuum distillation gave the product which was purified by column chromatography to give about 3.79 g of compound 6.

(Synthesis of Compound 7)

Approximately 4 g of 4-iodophenol (4-iodophenol), about 0.29 g of pyridinium p - toluenesulfonate, dihydro-pyran of about 2.48 g of (pyridinium p-toluenesulfonate) in was dissolved in dichloromethane, 0 ℃ (3 , 4-Dihydro-2H-pyran) was slowly added dropwise, and the mixture was stirred at room temperature for 4 hours. The reaction solution was quenched with triethylamine, diluted with dichloromethane, and washed with distilled water and brine. Then, the organic layer was collected, chemically dried, and the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 5.33 g of Compound 7.

(Synthesis of Compound 8-1)

About 1.3 g of compound 7 and about 2.8 g of the above compound 6-1, about 0.17 g of CuI, and about 0.14 g of PdCl ₂ (PPh ₃ ) ₂ were dissolved in N, N-diisopropylethylamine and tetrahydrofuran Furan in a 1: 1 mixed solvent, and then stirred at room temperature for one day. To this reaction solution, a saturated ammonium chloride solution was added dropwise, diluted with ethyl acetate, and washed with distilled water and brine. Then, the organic layer was collected, chemically dried, and the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 3.2 g of Compound 8-1.

(Synthesis of compound RM-01)

About 10 g of Compound 8-1 and about 2 g of p-toluenesulfonic acid were placed in tetrahydrofuran and stirred at room temperature for one day. The reaction solution was diluted with ethyl acetate, washed with distilled water and brine, and the organic layer was collected, chemically dried, and the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 3.5 g of the compound RM-01 of the above formula (4). The NMR spectrum of the compound RM-01 of the obtained compound (4) was as follows.

¹ H NMR (CDCl ₃ , standard TMS)? (Ppm):

Dd), 5.59 (1H, dd), 5.35 (2H, d), 8.04 (2H, d) (2H, t), 2.33 (1H, t), 2.32 (2H, t) (2H, dd), 2.12 (2H, dd), 1.75 (8H, m), 1.66 (4H, m), 1.60 (4H, m), 1.54 ), 0.99 (2H, q), 0.88 (3H, t)

Then, the structure of the compound RM-01 of the formula (4) was observed with a polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that the compound RM-01 of the formula (4) forms a nematic phase at a temperature range of about 80 to 110 ° C.

Example 2: Synthesis of compound RM-02

[Chemical Formula 5]

Compound RM-02 of Formula 5 was synthesized according to the reaction mechanism shown in Reaction Scheme 1 above.

(Synthesis of Compound 6-2)

(4R) -4 - ((4- (acryloyloxy) -butoxy) carbonyl) cyclohexanecarboxylic acid [(1R, - ((4- (acryloyloxy)) - carbonyl) cyclohexanecarboxylic acid [(1r, 4r) -4 - [(hexyl) oxy]) carbonyl) cyclohexanecarboxylic acid] was used in place of [(hexyloxy) carbonyl] cyclohexanecarboxylic acid].

(Synthesis of Compound 8-2)

In the same manner as in Example 1, except that Compound 6-2 was used instead of Compound 6-1, about 3.4 g of compound 8-2 was obtained.

(Synthesis of compound RM-02)

In the same manner as in Example 1, except that Compound 8-2 was used instead of Compound 8-1, about 3.6 g of the compound RM-02 of Formula 5 was obtained. The obtained NMR spectrum of the compound RM-02 of the above formula (5) was as follows.

¹ H NMR (CDCl ₃ , standard TMS)? (Ppm):

(1H, dd), 8.05 (2H, d), 7.29 (2H, d), 7.12 (1H, t), 2.32 (2H, dd), 2.12 (2H, t), 4.16 (2H, dd), 1.75 (8H, m), 1.66 (4H, m), 1.60 (4H, m), 1.54 ), 0.98 (2H, q), 0.88 (3H, t)

Then, the structure of the compound RM-02 of Formula 5 was observed with a polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that the compound RM-02 of Formula 5 formed a nematic phase at a temperature range of about 90 to 120 ° C.

Example 3: Synthesis of compound RM-03

[Chemical Formula 6]

Compound RM-03 of Formula 6 was synthesized according to the reaction mechanism shown in Scheme 1 above.

(Synthesis of Compound 6-3)

(4R) -4 - ((4- (acryloyloxy) -butoxy) carbonyl) cyclohexanecarboxylic acid [(1R, - ((4- (acryloyloxy) - carbonyl) cyclohexanecarboxylic acid [(1r, 4r) -4 - [(octyl) oxy]) carbonyl) cyclohexanecarboxylic acid] was used, and about 4.1 g of Compound 6-3 was obtained in the same manner as in Example 1.

(Synthesis of Compound 8-3)

In the same manner as in Example 1, except that Compound 6-3 was used instead of Compound 6-1, about 3.5 g of Compound 8-3 was obtained.

(Synthesis of compound RM-03)

In the same manner as in Example 1, except that Compound 8-3 was used instead of Compound 8-1, about 4 g of the compound RM-03 of Formula 6 was obtained. The obtained NMR spectrum of the compound RM-03 of the above formula (6) was as follows.

¹ H NMR (CDCl ₃ , standard TMS)? (Ppm):

Dd), 5.59 (1H, dd), 5.35 (2H, d), 8.04 (2H, (2H, t), 2.33 (1H, t), 2.32 (2H, t) (2H, dd), 2.12 (2H, dd), 1.75 (8H, m), 1.66 (4H, m), 1.60 (4H, m), 1.54 , m), 1.14 (4H), 0.98 (2H, q), 0.88 (3H, t)

Then, the structure of the compound RM-03 of Formula 6 was observed with a polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that the compound RM-02 of Formula 6 formed a nematic phase at a temperature range of about 90 to 115 ° C.

Production Examples 1 to 3

Using the liquid crystal compounds RM-01, RM-02 and RM-03 of Examples 1 to 3 respectively, liquid crystal compositions were prepared in the following manner.

First, 10% by weight of the liquid crystal compound (RM-01, RM-02 or RM-03) and the compound RM-257 [2-methyl- a composition comprising 15% by weight of acryloyloxy propoxy benzoate manufactured by XI'AN RUILIAN MODERN Co., Ltd, 5% by weight of Irgacure 369 (manufactured by Ciba-Geigy, Switzerland) as a photoinitiator and 70% by weight of toluene .

[Compound 7]

The liquid crystal composition was coated on a TAC (triacetylcellulose) film coated with a norbornene-based photo-alignment material by a roll coating method and then dried at about 80 ° C for 2 minutes to orient the liquid crystal compound. Thereafter, the film was irradiated with unpolarized UV using a high-pressure mercury lamp of 200 mW / cm 2 as a light source to fix the alignment state of the liquid crystal to produce an optical film.

The quantitative retardation value of each optical film was measured using an Axo scan (manufactured by Axomatrix). The results are shown in Table 1 below.

Comparative Preparation Example 1

An optical film was prepared in the same manner as in Production Example 1, except that the above compound RM-01 was not used and the compound RM257 was used in an amount of 25% by weight. The quantitative retardation value of each optical film was measured using an Axo scan (manufactured by Axomatrix). The results are shown in Table 1 below.

Production Example 1 Production Example 2 Production Example 3 Comparative Preparation Example 1 R ₄₅₀ / R ₅₅₀ 0.99 0.99 0.99 1.11 R ₅₅₀ 125 130 120 138

As can be seen from the above Table 1, the optical films according to Production Examples 1 to 3 using specific liquid crystal compounds according to the present invention had lower R _{450 values} than the optical films of Comparative Production Example 1 using only conventional liquid crystal compounds / R ₅₅₀ value, showing a similar level of R ₅₅₀ , indicating an inverse dispersion (or a flat dispersion) and an excellent orientation stability.

In particular, when an optical film produced using the polymerizable liquid crystal compound of the present invention is applied to an OLED-type display, the interference due to external light can be minimized, thereby achieving a more perfect black color.

Claims (6)

A polymerizable liquid crystal compound represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
A is an unsubstituted alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkynylene group having 2 to 6 carbon atoms;
L ₁ , L ₂ , and L ₃ are each independently a single bond or a divalent linking group, and at least one of L ₁ , L ₂ , and L ₃ is a divalent linking group;
E ₁ and E ₂ are each independently an unsubstituted aromatic group or heteroaromatic group having 6 to 20 carbon atoms;
D ₁ is an unsubstituted alkylene group having 1 to 12 carbon atoms;
D ₂ is an unsubstituted alkyl group having 1 to 12 carbon atoms;
R ₁ and R ₂ are each independently a cycloalkylene group having 3 to 12 carbon atoms;
G is a hydroxy group or an amine group.
J is a single substituent selected from the group consisting of the following formula (2);
(2)

n is an integer of 1 to 10; The method according to claim 1,
Wherein E ₁ and E ₂ are each independently a benzene ring, a naphthalene ring, or a phenanthrene ring. The method according to claim 1,
Wherein R ₁ and R ₂ are each independently a cyclohexane ring or a cyclohexene ring. The method according to claim 1,
The bivalent linking group is selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO- NR-CO-NR-, -O ( CH 2) x -, - (CH 2) x O-, -CH = CHCH 2 O-, -OCH 2 CH = CH-, - (CH 2) x COO-, _{-OCO (CH 2) x -,} - (CH 2) x OCO-O-, -OCO-O- (CH 2) x -, -SCH 2 -, -CH 2 S-, -CF 2 O-, _{-OCF 2 -, -CF 2 S-,} -SCF 2 -, - (CH 2) x -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CH = CH- , -C = C-, -CH = N-, -N = CH-, or -N = N-; R is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and x is independently an integer of 1 to 8. A polymerizable liquid crystal composition comprising a compound according to claim 1. An optical film formed using the composition according to claim 5.