KR20150037651A - Polymerizable liquid crystal compounds, liquid crystal composition comprising the compounds, and optical film comprising the composition - Google Patents

Abstract

The present invention relates to polymerizable liquid crystal compounds, and a liquid crystal composition and an optical film comprising the same. According to the present invention, provided are polymerizable liquid crystal compounds which can form a liquid crystal layer having normal wavelength distribution and high orientation stability. The optical film formed by using the polymerizable liquid crystal compounds can be suitably used for an anti-reflection film to a liquid crystal display or 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 to provide a polymerizable liquid crystal compound which can be suitably used in an antireflection film or the like by allowing the formation of a liquid crystal layer having a flat wavelength dispersion and a 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 -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, -C (= O) R 1, - NH ₂ , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , an alkenyl group having 2 to 6 carbon atoms, An acyl group having 2 to 4 carbon atoms, an alcohol group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms;

E ¹ , E ² , D ¹ , and D ² are each independently a single bond or a divalent linking group;

G ¹ and G ² are each independently a substituted or unsubstituted alicyclic group having 3 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 20 carbon atoms ego;

L ¹ and L ² are each independently -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, (= O) R ¹ , -OC (= O) R ¹ , -NH ² , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , substituted or unsubstituted silyl, substituted or unsubstituted carbyl or hydrocarbyl having 1 to 40 carbon atoms, or -S _p -P, wherein P is a polymerizable group, and S _p is a spacer group or Each of R ¹ and R ² is independently -H or alkyl having 1 to 12 carbon atoms, and at least one of L ¹ and L ² is -S _p -P;

m and n are each independently an integer of from 1 to 5, and when m or n is 2 or more, each repeating unit of - (D ¹ -G ¹ ) - or - (G ² -D ² ) May be the same or different from each other.

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

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 in the specification, the term "comprising " embodies specific features, regions, integers, steps, operations, elements or components and does not exclude the addition of other specified features, regions, integers, steps, operations, elements, It does not.

On the other hand, "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.

"Mesogenic Group" means a group having the ability to induce liquid crystalline phase behavior.

A "spacer group" is known to those skilled in the art and is described, for example, in C. C. < RTI ID = 0.0 > Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. The spacer group refers to a flexible organic group connecting the mesogen group to the polymerizable group.

"Carbyl group" includes one or more carbon atoms (eg, -C≡C-) that are free of any non-carbon atoms or alternatively contains one or more non-carbon atoms (eg, N, O, S, P, Si Quot; means any monovalent or multivalent organic radical moiety, including one or more carbon atoms (e.g., carbonyl) in combination with one or more carbon atoms. "Hydrocarbyl group" means a carbyl group additionally containing one or more H atoms and optionally containing one or more heteroatoms (eg, N, O, S, P, Si).

I. Polymerizable  Liquid crystal compound

According to one embodiment of the invention, there is provided a polymerizable liquid crystal compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

A is -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, -C (= O) R 1, - NH ₂ , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , an alkenyl group having 2 to 6 carbon atoms, An acyl group having 2 to 4 carbon atoms, an alcohol group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms;

E ¹ , E ² , D ¹ , and D ² are each independently a single bond or a divalent linking group;

G ¹ and G ² are each independently a substituted or unsubstituted alicyclic group having 3 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 20 carbon atoms ego;

L ¹ and L ² are each independently -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, (= O) R ¹ , -OC (= O) R ¹ , -NH ² , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , substituted or unsubstituted silyl, substituted or unsubstituted carbyl or hydrocarbyl having 1 to 40 carbon atoms, or -S _p -P, wherein P is a polymerizable group, and S _p is a spacer group or Each of R ¹ and R ² is independently -H or alkyl having 1 to 12 carbon atoms, and at least one of L ¹ and L ² is -S _p -P;

m and n are each independently an integer of from 1 to 5, and when m or n is 2 or more, each repeating unit of - (D ¹ -G ¹ ) - or - (G ² -D ² ) May be the same or different from each other.

As a result of the continuous experiments of the present inventors, it has been surprisingly confirmed that the polymerizable liquid crystal compound having the structure as shown in the above formula (1) enables the formation of a liquid crystal layer having a flat wavelength dispersion and a further improved alignment stability upon coating . 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 an embodiment of the present invention, A in the formula (1) is a group that enables intermolecular interactions (preferably, intermolecular bonding) of a polymerizable liquid crystal compound and can exhibit improved orientation stability through interaction with other molecules . A thus enabling intermolecular interaction is, preferably, -F, -Cl, -Br, -I , -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R ² , -C (= O) R ¹ , -NH ₂ , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , An alkynyl group having 2 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an alcohol group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, wherein R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms. Particularly, it is advantageous that the above-mentioned A is an alkynyl group having 2 to 6 carbon atoms, so that an improved orientation stability can be manifested through easy intermolecular interaction.

According to an embodiment of the present invention, E ¹ , E ² , D ¹ , and D ² in Formula 1 may each independently be a single bond or a divalent linking group. Specifically, E ¹ , E ² , D ¹ and D ² each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -O- ^{CO-NR 1 -, -NR 1} -CO-, -NR 1 -CO-NR 1 -, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CF 2 O- _{, -OCF 2 -, -CF 2 S-} , -SCF 2 -, -CH 2 CH 2 -, - (CH 2) 3 -, - (CH 2) 4 -, -CF 2 CH 2 -, -CF 2 _{CH 2 -, -CH = CH-,} -CY 1 = CY 2 -, -CH = N-, -N = CH-, -N = N-, -CH = CR 1 -, -C≡C-, - CH = CH-COO-, -OCO-CH = CH-, or -CR ¹ R ² -; Y ¹ and Y ² are each independently -H, -F, -Cl, -CN, or -R ¹ ; R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms.

In Formula 1, G ¹ and G ² each independently represent a substituted or unsubstituted alicyclic group having 3 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon number 6 To 20 heteroaromatic groups.

Preferably, G ¹ and G ² are each independently selected from the group consisting of trans-1,4-cyclohexylene, 1,4-phenylene, 1,5-naphthylene, and 2,6-naphthylene Being; Wherein the phenylene and naphthylene hydrogen is -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2 contained in the - ^{C (= O) R 1,} -NH 2, -SH, -SR 1, -SO 3 H, -SO 2 R 1, -OH, -NO 2, substituted or non-substituted by -CF _3, or -SF ₃ Lt; / RTI > R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms.

In Formula 1, L ¹ and L ² each independently represent -H, -F, -Cl, -Br, -I, -CN, -NNC, -OCN, -SCN, -C ^{) NR 1 R 2, -C (} = O) R 1, -OC (= O) R 1, -NH 2, -SH, -SR 1, -SO 3 H, -SO 2 R 1, -OH, - NO ₂ , -CF ₃ , -SF ₃ , substituted or unsubstituted silyl, substituted or unsubstituted carbamoyl or hydrocarbyl having 1 to 40 carbons, and -S _p -P. Provided that at least one of L ¹ and L ² is -S _p -P. Wherein P is a polymerizable group, S _p is a spacer group or a single bond, and R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms.

As a non-limiting example, L ¹ and L ² may be selected from straight, branched or cyclic alkyl groups of 1 to 25 carbon atoms which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, At least one non-adjacent CH ₂ group is independently selected from the group consisting of -O-, -S-, -NH-, -NR ¹ -, SiR ¹ R ² -, -CO-, -COO-, -OCO-, -OCO -O-, -S-CO-, -CO- S-, -SO 2 -, -CO-NR 1 -, -NR 1 -CO-, -NR 1 -CO-NR 1 -, -CY 1 = CY ² -, or -C? C-. Wherein Y ¹ and Y ² are each independently -H, -F, -Cl, -CN, or -R ¹ , and R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms .

L ¹ and L ² are each independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, oxalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkynyl of 2 to 20 carbon atoms, A silyl of 20 to 20 carbon atoms, an ester of 1 to 20 carbon atoms, an amino of 1 to 20 carbon atoms, and a fluoroalkyl of 1 to 20 carbon atoms.

,

, 또는

일 수 있다. 여기서, 상기 Z¹ 내지 Z³은 각각 독립적으로 -H, -F, -Cl, -CN, -CF₃, 페닐, 또는 탄소수 1 내지 5의 알킬이고, 상기 Phe는 -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C(=O)NR¹R², -C(=O)R¹, -NH², -SH, -SR¹, -SO₃H, -SO₂R¹, -OH, -NO₂, -CF₃, 또는 -SF₃에 의해 치환 또는 비치환된 1,4-페닐렌이고, 상기 a 및 b는 각각 독립적으로 0 또는 1이다.Further, in one example _p -S -P of said L ¹ and L ^2, wherein P is a polymerizable group, ^{_{preferably, CH 2 = CZ 1 -COO-,}} CH 2 = CZ 1 -CO-, CH 2 = _{^{CZ 2 - (O) a -}} , CH 3 -CH = CH-O-, (CH 2 = CH) 2 CH-OCO-, (CH 2 = CH-CH 2) 2 CH-OCO-, (CH 2 = _{CH) 2 CH-O-, (} CH 2 = CH-CH 2) 2 N-, (CH 2 = CH-CH 2) 2 N-CO-, HO-CZ 1 Z 2 -, HS-CZ 1 Z 2 ^{-, HZ 1 N-, HO-} CZ 1 Z 2 -NH-, CH 2 = CZ 1 -CO-NH-, CH 2 = CH- (COO) a -Phe- (O) b -, CH 2 = CH - (CO) _a -Phe- (O) _b- , Phe-CH = CH-, HOOC-, OCN-, Z ¹ Z ² Z ³ Si-,

,

, or

Lt; / RTI > Wherein Z ¹ to Z ³ are each independently -H, -F, -Cl, -CN, -CF ₃ , phenyl, or C 1-5 alkyl, and Phe is -F, -Cl, -Br (= O) NR ¹ R ² , -C (= O) R ¹ , -NH ² , -SH, -SR ¹ , Phenylene which is unsubstituted or substituted by -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , or -SF ₃ , each of a and b is independently 0 Or 1.

And, "the formula -X'-S _p such that -P 'are selected from the above -S _p -P S _p is the _p -S -P -X'-S _p, the S _p' is -F, -Cl, -Br, -I, -CN, or a mono-substituted or multi-substituted alkylene group having 1 to 20 carbon atoms, at least one in the alkylene -CH ₂ - group can -O-, -S-, -NH -, -NR ¹ -, SiR ¹ R ² -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ¹ -CO-O -, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ -, -CH = CH-, or -C≡C-. X 'represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ¹ -, -NR ¹ -CO-, -NR ¹ - _{^{CO-NR 1 -, -OCH 2}} -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -OCF 2 -, -CF 2 O-, -SCF 2 -, -SF 2 O-, _{-CF 2 CH 2 -, -CF 2} CF 2 -, -CH = N-, -N = CH-, -N = N-, -CH = CR 1 -, -CY 1 = CY 2 -, -C≡ C-, -CH = CH-COO-, -OCO-CH = CH-, or a single bond. Wherein Y ¹ and Y ² are each independently -H, -F, -Cl, -CN, or -R ¹ , and R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms .

In Formula 1, m and n may each independently be an integer of 1 to 5. Here, when m or n is 2 or more, the repeating units of - (D ¹ -G ¹ ) - or - (G ² -D ² ) - which are repeated two or more times may be the same or different. For example, when m is 2, D ¹ or G ¹ contained in each repeating unit of - (D ¹ -G ¹ ) - (D ¹ -G ¹ ) - may be the same or different from each other in the above- Lt; / RTI >

As a non-limiting example, the polymerizable liquid crystal compound of Formula 1 may be a compound represented by RM-01 or RM-02 according to the following Examples. However, the polymerizable liquid crystal compound is not limited to the compounds RM-01 to RM-02, and may be implemented in various combinations in the above-described ranges.

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

II . Polymerizable  Liquid crystal composition

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

The polymerizable liquid crystal composition may be a composition in which the compound represented by Formula 1 is dissolved in a solvent together with a polymerization initiator. 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. It is preferable that the compound represented by the formula (1) is included in an amount of 5% by weight of the total liquid crystal compound, It can be advantageous from the side.

III . Optical film

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

In particular, the above optical film may include a liquid crystal layer capable of exhibiting flat wavelength dispersion and exhibiting a high birefringence and an improved orientation stability, by including the polymerizable liquid crystal compound described above.

The optical film can be 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 the aligned state, and then irradiating the polymerizable liquid crystal composition with an energy ray.

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, and the like 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.

The polymerizable liquid crystal compound according to the present invention enables the formation of a liquid crystal layer having a high degree of orientation stability while having a flat wavelength dispersion upon coating a composition containing the polymerizable liquid crystal compound. 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.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a scheme for the synthesis of a polymerizable liquid crystal compound according to an embodiment of the present invention.

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: Compound RM Synthesis of -01

The compound RM-01 (n = 4) was synthesized according to Scheme shown in Fig.

(Synthesis of Compound 2-a)

Approximately 44 g of triethylamine (TEA) was added to about 46 g of compound 1-a (1,4-butanediol) and about 500 ml of dichloromethane. Then, a solution of about 20 g of acryloyl chloride in about 300 ml of dichloromethane was slowly added to the solution at about 0 캜, and then the temperature was raised to room temperature and stirred for about 12 hours.

Then, a brine solution was added thereto, and an organic solution portion was extracted with dichloromethane. The solvent contained in the extracted organic solution was distilled off under reduced pressure and purified by column chromatography to obtain about 21 g of compound 2-a.

(Synthesis of Compound 3-a)

Approximately 51 g of (1r, 4r) -cyclohexane-1,4-dicarboxylic acid was dissolved in 1 L of dichloromethane and then about 57 g of EDC (1-Ethyl-3- (3- dimethylaminopropyl) carbodiimide) 5 g of DMAP (4-dimethylaminopyridine) was added thereto, followed by stirring for 1 hour. To this solution, about 21 g of the compound 2-a and about 34 g of diisopropylamine dissolved in about 500 ml of dichloromethane were slowly added over about 1 hour, and then about 18 hours Lt; / RTI >

Then, a brine solution was added thereto, and an organic solution portion was extracted with dichloromethane. The solvent contained in the extracted organic solution was distilled off under reduced pressure and purified by column chromatography to obtain about 26 g of compound 3-a.

(Synthesis of Compound 5)

About 25 g of Compound 4 (4- (4-hydroxyphenyl) cyclohexanone) and about 20.38 g of N, N-diisopropylethylamine were dissolved in dichloromethane, and about 11.64 g Chloro (methoxy) methane was slowly added dropwise and stirred for about 2 hours. The reaction solution was washed with distilled water and brine solution, and the organic fraction was collected and chemically dried, and then the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 19 g of Compound 5.

(Synthesis of Compound 6)

About 17.1 g of ethynyltrimethylsilane and about 20.24 g of N, N, N ', N'-tetramethylethylenediamine were dissolved in tetrahydrofuran THF), and then about 50 ml of n-butyl lithium in 2.5 M hexane was added dropwise at about -78 ° C. and under a nitrogen atmosphere, and the mixture was stirred for about 1 hour. To the solution was added dropwise a tetrahydrofuran solution containing about 37 g of Compound 5, and the mixture was stirred at about -78 캜 for about 2 hours. After the temperature of the reaction solution was raised to room temperature, distilled water was added thereto and extracted with ethyl acetate. The organic portion was collected and chemically dried and then the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 30 g of Compound 6.

(Synthesis of Compound 7)

Approximately 30 g of Compound 6 was dissolved in tetrahydrofuran (THF), followed by dropwise addition of 45 ml of a 1 molar solution of tetrabutylammonium fluoride (TBAF) solution, which was stirred for about 24 hours. Distilled water was added to the reaction solution, which was extracted with ethyl acetate. The organic portion was collected and chemically dried and then the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain about 16 g of Compound 7.

(Synthesis of Compound 9)

About 10.4 grams of Compound 7, about 8 grams of Compound 8 (4- (methoxymethoxy) benzoic acid), about 9.8 grams of 4- (dimethylamino) pyridine), and about 11.5 grams of EDC 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide) was dissolved in dichloromethane, and the mixture was stirred at room temperature for about 24 hours. The reaction solution was diluted with dichloromethane, washed with distilled water and brine solution, and chemically dried. The product was obtained through filtration and vacuum distillation and was purified by column chromatography to obtain about 14 g of Compound 9.

(Synthesis of Compound 10)

About 14 g of Compound 9 was dissolved in tetrahydrofuran (THF), and a 6N hydrochloric acid solution was added dropwise thereto, followed by stirring at room temperature for about 24 hours. The reaction solution was washed with sodium bicarbonate solution and brine solution and chemically dried. The product was obtained by filtration and vacuum distillation, which was purified by column chromatography to give about 10 g of compound 10.

(Synthesis of compound RM-01)

About 5 g of compound 10, about 9.76 g of compound 3-a, about 5.47 g of 4- (dimethylamino) pyridine), and about 7.12 g of EDC (1-Ethyl- 3-dimethylaminopropyl) carbodiimide) was dissolved in dichloromethane, and the mixture was stirred at room temperature for about 24 hours. The reaction solution was diluted with dichloromethane, washed with distilled water and brine solution, and chemically dried. The product was obtained through filtration and vacuum distillation and was purified by column chromatography to obtain about 1.65 g of the compound RM-01.

NMR spectrum of the obtained compound RM-01 is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.06 (2H, d), 7.25 (2H, d), 7.14 (2H, d), 7.00 (2H, d), 6.42 (2H, d) (2H, d), 2.50 (2H, d), 2.54 (2H, d) (2H, m), 1.76 (8H, m), 1.56 (4H, m), 2.16

Example  2: Compound RM Synthesis of -02

The compound RM-02 (n = 6) was synthesized according to Scheme shown in Fig.

(Synthesis of Compound 2-b)

The same procedure as in the synthesis of the compound 2-a of Example 1 was carried out except that the compound 1-b (1,6-hexanediol) was used instead of the compound 1-a (1,4-butanediol) .

(Synthesis of Compound 3-b)

About 26 g of the compound 3-b was obtained in the same manner as in the synthesis of the compound 3-a of Example 1, except that the above compound 2-b was used in place of the compound 2-a.

(Synthesis of compound RM-02)

About 4.8 g of the compound RM-02 was obtained in the same manner as in the synthesis of the compound RM-01 of Example 1, except that about 8.52 g of the above compound 3-b was used instead of the compound 3-a.

NMR spectrum of the obtained compound RM-02 is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.06 (2H, d), 7.24 (2H, d), 7.14 (2H, d), 7.00 (2H, d), 6.40 (2H, dd) (2H, d), 2.50 (2H, dd), 3.16 (2H, dd) (2H, m), 1.66 (2H, m), 1.22 (2H, m), 2.33 (8H, m)

Manufacturing example  One

10% by weight of the above compound RM-01, 2-methyl-1,4-phenylene bis (4- (3- (acryloyloxy) propoxy) benzoate represented by the following RM257, manufactured by XI'AN RUILIAN MODERN Co., Ltd.), 5% by weight of photoinitiator Irgacure 369 (manufactured by Ciba-Geigy of Switzerland), and 70% by weight of toluene.

[Compound RM257]

The liquid crystal composition was coated on a TAC (triacetylcellulose) film coated with a norbornene-based photo-alignment material by a bar 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.

Manufacturing example  2

An optical film was prepared in the same manner as in Production Example 1 except that the compound RM-02 (Preparation Example 2) was used in place of the compound RM-01.

Manufacturing example  3

An optical film was prepared in the same manner as in Production Example 1, except that a mixture of 5% by weight of the compound RM-01 and 5% by weight of the compound RM-02 was used instead of the compound RM-01.

Control Example

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.

Test Example

For each optical film according to Production Examples, a quantitative retardation value was measured using Axoscan (manufactured by Axomatrix). At this time, the thickness was independently measured, and the retardation value (DELTA nd) was calculated from the obtained value Respectively. The results are shown in Table 1 below.

Phase difference value Production Example 1 Production Example 2 Production Example 3 Control Example DELTA n (450 nm) / DELTA n (550 nm) 1.00 0.99 1.00 1.11 DELTA n d (550 nm) 120 136 140 138

As can be seen from the above Table 1, the optical films according to Production Examples 1 to 3 exhibited low Δn (450 nm) / Δn (550 nm) values and comparable levels Δn D (550 nm). Thus, it was confirmed that the optical films of Production Examples 1 to 3 exhibited flat wavelength dispersion and high orientation stability.

Claims (8)

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

In Formula 1,
A is -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, -C (= O) R 1, - NH ₂ , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , an alkenyl group having 2 to 6 carbon atoms, An acyl group having 2 to 4 carbon atoms, an alcohol group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms;
E ¹ , E ² , D ¹ , and D ² are each independently a single bond or a divalent linking group;
G ¹ and G ² are each independently a substituted or unsubstituted alicyclic group having 3 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 20 carbon atoms ego;
L ¹ and L ² are each independently -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, (= O) R ¹ , -OC (= O) R ¹ , -NH ² , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ , -SF ₃ , substituted or unsubstituted silyl, substituted or unsubstituted carbyl or hydrocarbyl having 1 to 40 carbon atoms, or -S _p -P, wherein P is a polymerizable group, and S _p is a spacer group or Each of R ¹ and R ² is independently -H or alkyl having 1 to 12 carbon atoms, and at least one of L ¹ and L ² is -S _p -P;
m and n are each independently an integer of from 1 to 5, and when m or n is 2 or more, each repeating unit of - (D ¹ -G ¹ ) - or - (G ² -D ² ) May be the same or different from each other.
The method according to claim 1,
Wherein A is an alkynyl group having 2 to 6 carbon atoms.
The method according to claim 1,
Each of E ¹ , E ² , D ¹ and D ² is independently a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^{1 -, -NR 1 -CO-, -NR} 1 -CO-NR 1 -, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF _{2 -, -CF 2 S-, -SCF} 2 -, -CH 2 CH 2 -, - (CH 2) 3 -, - (CH 2) 4 -, -CF 2 CH 2 -, -CF 2 CH 2 - ^{, -CH = CH-, -CY 1 =} CY 2 -, -CH = N-, -N = CH-, -N = N-, -CH = CR 1 -, -C≡C-, -CH = CH -OCO-CH = CH-, or -CR ¹ R ² -, wherein Y ¹ and Y ² are each independently -H, -F, -Cl, -CN, or -R ¹ , R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms.
The method according to claim 1,
Wherein G ¹ and G ² are each independently selected from the group consisting of trans-1,4-cyclohexylene, 1,4-phenylene, 1,5-naphthylene and 2,6-naphthylene,
Wherein the phenylene and naphthylene hydrogen is -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2 contained in the - ^{C (= O) R 1,} -NH 2, -SH, -SR 1, -SO 3 H, -SO 2 R 1, -OH, -NO 2, substituted or non-substituted by -CF _3, or -SF ₃ And R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms.
The method according to claim 1,
Wherein P is ^{_{CH 2 = CZ 1 -COO-, CH}} 2 = CZ 1 -CO-, CH 2 = CZ 2 - (O) a -, CH 3 -CH = CH-O-, (CH 2 = CH) 2 _{CH-OCO-, (CH 2 =} CH-CH 2) 2 CH-OCO-, (CH 2 = CH) 2 CH-O-, (CH 2 = CH-CH 2) 2 N-, (CH 2 = CH _{-CH 2) 2 N-CO-,} HO-CZ 1 Z 2 -, HS-CZ 1 Z 2 -, HZ 1 N-, HO-CZ 1 Z 2 -NH-, CH 2 = CZ 1 -CO-NH _{-, CH 2 = CH- (COO} ) a -Phe- (O) b -, CH 2 = CH- (CO) a -Phe- (O) b -, Phe-CH = CH-, HOOC-, OCN- , Z ¹ Z ² Z ³ Si-,

,

, or

ego,
Wherein Z ¹ to Z ³ are each independently -H, -F, -Cl, -CN, -CF ₃ , phenyl, or alkyl of 1 to 5 carbon atoms,
The Phe is -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2, -C (= O) R 1, Phenylene which is unsubstituted or substituted by -NH ² , -SH, -SR ¹ , -SO ₃ H, -SO ₂ R ¹ , -OH, -NO ₂ , -CF ₃ or -SF ₃ ego,
Wherein each of a and b is independently 0 or 1.
The method according to claim 1,
Wherein S _p is selected from 'the formula -X'-S _p such that -P' is -S _p -P -X'-S _p,
Wherein S _p 'is an alkylene having 1 to 20 carbon atoms which is mono- or polysubstituted by -F, -Cl, -Br, -I, or -CN, wherein at least one -CH ₂ - group in the alkylene is -O ^{-, -S-, -NH-, -NR 1} -, SiR 1 R 2 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S- , -NR ¹ -CO-O-, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ -, -CH = CH- or -C≡C-,
X 'represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ¹ -, -NR ¹ -CO-, -NR ¹ -CO- NR ¹ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -OCF ₂ -, -CF ₂ O-, -SCF ₂ -, -SF ₂ O-, -CF _{2 CH 2 -, -CF 2 CF} 2 -, -CH = N-, -N = CH-, -N = N-, -CH = CR 1 -, -CY 1 = CY 2 -, -C≡C- , -CH = CH-COO-, -OCO-CH = CH-, or a single bond,
Y ¹ and Y ² are each independently -H, -F, -Cl, -CN, or -R ¹ ,
Wherein R ¹ and R ² are each independently -H or alkyl having 1 to 12 carbon atoms.
A polymerizable liquid crystal composition comprising a compound according to claim 1.
An optical film formed using the composition according to claim 7.

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