KR101659071B1 - Polymerizable liquid crystal compounds, liquid crystal composition comprising the compounds, and optically anisotropic body comprising the composition - Google Patents

Abstract

The present invention relates to a polymerizable liquid crystal compound, a liquid crystal composition comprising the same, and an optical anisotropic medium. According to the present invention, an optically anisotropic substance having a thin thickness while exhibiting a stable inverse wavelength dispersion using the polymerizable liquid crystal compound can be produced by a more simplified method, and it can be produced by a liquid crystal display device such as a broad band? / 4 wave plate And can be applied as an optical film for use.

Description

POLYMERIZABLE LIQUID CRYSTAL COMPOUNDS, LIQUID CRYSTAL COMPOSITION COMPOSITION COMPOUNDS, AND OPTICALLY ANISOTROPIC BODY 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 comprising the same, and an optical anisotropic medium.

A phase retarder is a type of optical element that changes the polarization state of light passing through it. It is also called a wave plate. When the electromagnetic wave passes through the phase retarder, the polarization direction (electric field vector direction) becomes the sum of two components (normal and extraordinary rays) parallel or perpendicular to the optical axis, and the vector sum of the two components depends on the birefringence and thickness of the phase retarder So that the polarization direction after passing is different. At this time, changing the polarization direction of light by 90 degrees is called a quarter-wave plate (λ / 4), and a 180 ° change is called a half-wave plate (λ / 2).

At this time, the retardation value of the phase retarder depends on the wavelength, and the wavelength dispersion of the retardation value is classified into normal wavelength dispersion, flat wavelength dispersion, and reverse wavelength dispersion.

Among them, a phase retarder exhibiting reverse wavelength dispersion is most useful because it has a predetermined retardation (? / 4,? / 2, etc.) in a wide wavelength band, and most phase retarders formed of a conventional resin film exhibit a constant wavelength dispersion .

Various studies have been conducted to solve such problems. For example, Japanese Patent Application Laid-Open No. 1998-068816, Japanese Laid-Open Patent Publication No. 1998-090521, Japanese Laid-Open Patent Application No. 1999-052131, 002841 discloses a layered phase retarder in which a plurality of optically anisotropic layers are laminated. However, a laminate type phase retarder having a structure in which a large number of optically anisotropic layers are laminated has a disadvantage in that the manufacturing yield is low and the manufacturing cost is high, since complicated procedures for arranging a plurality of films are required while controlling optical orientation in manufacturing.

On the other hand, Japanese Patent Application Laid-Open No. 2002-221622 discloses a method of manufacturing a wide-band? / 4 wave plate including only one phase retarder by inducing inverse dispersion through stretching of a film. It is disadvantageous in that it is not suitable for a liquid crystal display device in which a thin layer is required.

Japanese Patent Application Laid-Open No. 2002-267838 discloses a method of using a liquid crystal composition comprising a rod-shaped liquid crystal compound and a non-liquid crystalline substance oriented vertically to the long axis of the compound, for the purpose of producing a thin-film broadband wave plate . However, in the case of the above composition, reverse wavelength dispersion is not induced when the mixing ratio of the non-liquid crystal material is low, and when the mixing ratio is high, the liquid crystal properties of the composition itself are lost.

Accordingly, it is desired to develop a thin broadband phase retarder that can exhibit a stable inverse wavelength dispersion. Particularly, there is a desperate need for a liquid crystal compound capable of manufacturing such a phase retarder by a more simplified method.

Accordingly, the present invention is to provide a novel polymerizable liquid crystal compound which makes it possible to produce an optically anisotropic substance exhibiting reverse wavelength dispersion by a more simplified method.

The present invention also provides a polymerizable liquid crystal composition comprising the above compound.

Further, the present invention is to provide an optically anisotropic material comprising a polymer of the polymerizable liquid crystal composition.

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 ¹ to A ⁸ are each independently O, S, or Se;

D ¹ to D ⁴ are each independently N, P, or As;

E ¹ to E ⁴ and J ¹ to J ⁴ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a bivalent cyclic group having at least one aromatic ring or aliphatic ring or heterocyclic ring, Combination;

G ¹ to G ⁴ are each independently a single bond or a divalent linking group;

L ¹ to L ⁴ each independently represent a hydrogen group or a polymerizable group;

M is an alkynylene group having 2 to 6 carbon atoms, -CR ¹ ═CR ² -, a substituted or unsubstituted aromatic or heteroaromatic linking group, or a combination thereof, wherein R ¹ and R ² are each independently H, F, Cl, CN, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms;

m, n, and p are each independently an integer of 1 to 5;

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

According to another embodiment of the present invention, there is provided an optically anisotropic material comprising a cured product or polymer of the polymerizable liquid crystal compound.

According to the present invention, an optically anisotropic substance having a thin thickness while exhibiting a stable inverse wavelength dispersion using the polymerizable liquid crystal compound can be produced by a more simplified method, and it can be produced by a liquid crystal display device such as a broad band? / 4 wave plate And can be applied as an optical film for use.

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

Prior to that, unless explicitly stated, the term "including" or "containing" throughout the specification refers to including any element (or component) without any limitation, Can not be interpreted as excluding.

On the other hand, as a result of repeated studies on liquid crystal compounds, the present inventors have found that when a polymerizable liquid crystal compound having a chemical structure represented by Chemical Formula 1 below is used, an optically anisotropic material having a thin thickness, And the present invention has been completed.

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 ¹ to A ⁸ are each independently O, S, or Se;

D ¹ to D ⁴ are each independently N, P, or As;

E ¹ to E ⁴ and J ¹ to J ⁴ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a bivalent cyclic group having at least one aromatic ring or aliphatic ring or heterocyclic ring, Combination;

G ¹ to G ⁴ are each independently a single bond or a divalent linking group;

L ¹ to L ⁴ each independently represent a hydrogen group or a polymerizable group;

M is an alkynylene group having 2 to 6 carbon atoms, -CR ¹ = CR ² -, a substituted or unsubstituted aromatic or heteroaromatic linking group, or a combination thereof, wherein R ¹ and R ² are each independently H, F, Cl, CN, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms;

m, n, and p are each independently an integer of 1 to 5;

The polymerizable liquid crystal compound represented by the above formula (1) comprises two main chains connecting an aryl group between two maleimide derivatives, and the two main chains have a structure connected to each other by the M.

According to the present invention, in the above formula (1), A ¹ to A ⁸ each independently may be a Group 16 element (VIA) non-metallic element; Preferably oxygen (O), sulfur (S) or selenium (Se); More preferably oxygen (O).

In Formula 1, D ¹ to D ⁴ may each independently be a Group 15 element (VA) non-metallic element; Preferably nitrogen (N), phosphorus (P) or arsenic (As); And more preferably nitrogen (N).

In Formula 1, each of E ¹ to E ⁴ and J ¹ to J ⁴ is independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a divalent group having at least one aromatic ring or aliphatic ring or heterocyclic ring A cyclic group, or a combination thereof. According to the invention, the E ¹ to E ^4, and J ¹ to J ⁴ are each independently -CH _{2 -, - (CH 2) 2} -, - (CH 2) 3, - (CH 2) 4 -, - _{(CH 2) 5 -, -} (CH 2) 6 -, -Ph-, -Ph (CH 3) -, -Ph-CH 2 -, -Ph- (CH 2) 2 -, -Ph- (CH 2 _{) 3 -, - (Ph)} 2 -, - (Ph) 2 -CH 2 -, - (Ph) 2 - (CH 2) 2 - and the like; Wherein Ph is a phenyl group.

In Formula 1, G ¹ to G ⁴ each independently represents a single bond or a divalent linking group. The above-mentioned 'linking group having 2 or more valences' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR-, -NR- _{CO-NR-, -OCH 2 -,} -CH 2 O-, -SCH--, -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 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -C = C- or - C≡C-, wherein each R may independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

In the above formula (1), L ¹ to L ⁴ may each independently be hydrogen or a polymerizable group, wherein the 'polymerizable group' means any functional group capable of crosslinking or polymerizing, such as an unsaturated bond or a (meth) . ≪ / RTI > According to the present invention, each of L ¹ to L ⁴ may independently be a hydrogen group, an acrylate group, a methacrylate group, an epoxy group, or the like.

In the above formula (1), M is a bridge connecting two main chains, which is an alkynylene group having 2 to 6 carbon atoms, -CR ¹ ═CR ² -, a substituted or unsubstituted aromatic or heteroaromatic linking group, Wherein R ¹ and R ² are each independently H, F, Cl, CN, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms. Here, the 'substituted or unsubstituted aromatic or heteroaromatic linkage group' may be defined as meaning phenylene, biphenylene, or any divalent linking group including them, including diethynylbenzene or diethynylbiphenyl And the like. According to the present invention, M is selected from the group consisting of -C≡C-, -C≡CC≡C-, -C≡C-Ph-C≡C-, -C≡C-Ph-Ph-C≡C-, -C C-Ph-C? C-Ph-C? C-, etc., wherein Ph means a phenyl group.

Thus, the polymerizable liquid crystal compound of the present invention represented by the above formula (1) can be, for example, a polymerizable liquid crystal compound represented by the following formula (2)

(2)

In Formula 2, E ¹ to E ⁴ , J ¹ to J ⁴ , G ¹ to G ⁴ , L ¹ to L ⁴ , M and p are the same as in Formula 1, respectively.

Specific examples of the polymerizable liquid crystal compound of the present invention represented by the above formula (2) include the following formulas (3a) to (3f), but the present invention is not limited to the following illustrative compounds.

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

(3f)

On the other hand, the polymerizable liquid crystal compound of the present invention can be produced by applying a known reaction. Preferably, according to one embodiment of the present invention, the compound of Formula 1 may be prepared according to the following Reaction Scheme A, and a more detailed method of preparation is described in the Examples section. However, the process for producing the polymerizable liquid crystal compound according to the present invention is not limited to the following reaction formula A.

[Reaction Scheme A]

(Wherein X is a halogen group element and A ¹ to A ⁸ , D ¹ to D ⁴ , E ¹ to E ⁴ , J ¹ to J ⁴ , G ¹ to G ⁴ , L ¹ to L ⁴ , M, m, n and p are each the same as in the above formula (1)

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

The composition according to the present invention comprises a compound represented by the formula (1) which is a polymerizable liquid crystal monomer, and the compounds represented by the formula (1) may be homopolymerized or copolymerized singly or in combination of two or more.

In addition to the compound represented by the formula (1), the composition may further comprise an optional liquid crystal compound, 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.

In this case, the arbitrary liquid crystal compound may be mixed in an appropriate amount depending on the structure thereof. Preferably, the compound represented by the formula (1) according to the present invention is contained in an amount of 60 wt% It is more advantageous in terms of achieving one goal.

If necessary, the polymerizable liquid crystal composition may further contain a solvent, a polymerization initiator, a storage stabilizer, a liquid crystal alignment assistant, a dye, a pigment, and the like, and the additives may be conventional components in the technical field of the present invention , And the configuration thereof is not particularly limited.

According to another embodiment of the present invention, there is provided an optically anisotropic material comprising a cured product or a polymer of the polymerizable liquid crystal compound of formula (1).

The optically anisotropic material may include a cured product or polymer in which at least a part of terminal polymerizable groups of the polymerizable liquid crystal compound of Formula 1 is addition-polymerized or crosslinked.

Particularly, the optical anisotropic medium according to the present invention can exhibit an inverse wavelength dispersion satisfying the following formulas I and II by including a cured product or polymer of the above-mentioned polymerizable liquid crystal compound.

(Formula I)

DELTA n _{(450 nm )} / DELTA n _{(550 nm )} < 1.0

(Formula II)

? N _{(650 nm )} /? N _{(550 nm )} > 1.0

(In the above formulas I and II,? N (?) Means the specific refractive index at the wavelength? Within the liquid crystal phase)

As described above, by using the polymerizable liquid crystal compound of Formula 1 according to the present invention, an optically anisotropic material having a thin thickness and exhibiting reverse wavelength dispersion can be formed in a simpler process unlike the previous laminated optically anisotropic material.

On the other hand, the optically anisotropic material can be produced by coating and drying the polymerizable liquid crystal composition on a support, aligning the liquid crystal compound, and then irradiating ultraviolet light or the like.

Here, the support is not particularly limited, but a glass plate, a polyethyleneterephthalate film, a cellulose-based film, or the like can be used. As a method of applying the polymerizable liquid crystal composition to a support, known methods can be applied without any particular limitation. For example, a roll coating method, a spin coating method, a bar coating method, a spray coating method, and the like can be applied.

As a method of orienting the polymerizable liquid crystal composition, known methods such as rubbing the formed composition layer or applying a magnetic field or electric field to the formed composition layer may be applied.

The thickness of the optically anisotropic material may be adjusted depending on the application, and may be adjusted preferably in the range of 0.01 to 100 탆.

The optical anisotropic material of the present invention can be used as an optical element such as a retardation film, an optical compensation plate, an orientation film, a polarizer, a viewing angle enlargement plate, a reflection film, a color filter, a holographic element, a photo- have.

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  One

(1) Synthesis of Polymerizable Liquid Crystal Compound

A polymerizable liquid crystal compound (RD-01) was synthesized according to Reaction Scheme 1 below.

[Reaction Scheme 1]

First, a compound of the formula (a-1) (about 7.5 g) [Polym. Adv. Technol. (About 1.5 g), bis (triphenylphosphine) palladium (II) dichloride (about 0.47 g) of the formula (b-1), and copper iodide 122 mg) was dissolved in a mixed solution of triethylamine (100 ml) and dimethylformamide (50 ml). The solution was stirred at about 70 < 0 > C for 5 hours and cooled to precipitate crystals. The precipitate was collected by filtration, washed with methanol and dried to give the compound of formula (c-1) (about 6.5 g).

The compound of the above formula (c-1) (about 6 g) and the compound of the formula (d-1) (about 3.3 g) [Chem. Commun., 2010, 46, 5536] was dissolved in toluene (200 ml), and a Dean-Stark trap was installed, and the mixture was heated under reflux for 12 hours. After the solution was cooled to room temperature, a large amount of methanol was added to the reaction solution to precipitate a solid. Thereafter, the solvent was removed by filtration, and a compound of the formula (e-1) (about 11.1 g) was obtained through vacuum drying.

Then, the compound of the above formula (e-1) (about 9 g) was dissolved in dimethylacetamide (90 ml), cooled to 0 캜, acryloyl chloride (about 6.7 g) was added dropwise for 30 minutes, And stirred for 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous solution of sodium chloride. The organic portion was collected, and after chemical drying, the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain a compound of the formula (RD-01) (about 8.5 g).

The NMR spectrum of the obtained compound of formula (RD-01) is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.93 (2H, s), 7.42 (4H, m), 6.95 (8H, m), 6.65 (8H, m), 6.43 (4H, dd) , 6.05 (4H, dd), 5.80 (4H, dd), 4.89 (8H, s), 4.15 (8H, t), 3.95

Then, the texture of the compound of the above formula (RD-01) was observed with a polarizing microscope and the phase transition temperature was measured. As a result, an isotropic liquid crystal phase appeared when the temperature exceeded about 205 ° C. In this way, it has been confirmed that the compound of formula (RD-01) forms a nematic phase at a temperature range of about 170 ° C to 205 ° C.

(2) Production of optically anisotropic film (phase difference film)

A polymerizable liquid crystal composition comprising 25 parts by weight of the compound of the formula (RD-01), 5 parts by weight of Irgacure 907 (manufactured by Ciba-Geigy, Switzerland) as a photoinitiator and the rest of toluene was prepared based on 100 parts by weight of the total composition .

The liquid crystal composition was coated on a triacetyl cellulose 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 prepare a retardation film.

The quantitative retardation value of the produced retardation film was measured using Axoscan (manufactured by Axomatrix). At this time, the thickness was independently measured and the value of Δn was obtained from the obtained value. As a result, Δn (450 nm), Δn (550 nm), and Δn (650 nm) were measured to be 0.064, 0.071, and 0.074, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.90 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.04 and it was confirmed that the conditions according to the above formulas I and II were satisfied.

Example  2

(1) Synthesis of Polymerizable Liquid Crystal Compound

A polymerizable liquid crystal compound (RD-02) was synthesized according to the following Reaction Scheme 2.

[Reaction Scheme 2]

First, a compound of the formula (a-1) (about 7.5 g) [Polym. Adv. Technol. (About 1.5 g), bis (triphenylphosphine) palladium (II) dichloride (about 0.47 g) of the formula (b-1), and copper iodide 122 mg) was dissolved in a mixed solution of triethylamine (100 ml) and dimethylformamide (50 ml). The solution was stirred at about 70 < 0 > C for 5 hours and cooled to precipitate crystals. The precipitate was collected by filtration, washed with methanol and dried to give the compound of formula (c-1) (about 6.5 g).

The compound of the above formula (c-1) (about 6 g) and the compound of the formula (d-2) (about 3.3 g) [Chem. Commun., 2010, 46, 5536] was dissolved in toluene (200 ml), and a Dean-Stark trap was installed, and the mixture was heated under reflux for 12 hours. After the solution was cooled to room temperature, a large amount of methanol was added to the reaction solution to precipitate a solid. Thereafter, the solvent was removed by filtration, and the compound of the formula (e-2) (about 5.4 g) was obtained through vacuum drying.

Then, the compound of the above formula (e-2) (about 5 g) was dissolved in dimethylacetamide (90 ml), cooled to 0 캜, acryloyl chloride (about 6.7 g) was added dropwise for 30 minutes, And stirred for 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous solution of sodium chloride. The organic portion was collected, and after chemical drying, the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain a compound of the formula (RD-02) (about 4.1 g).

The NMR spectrum of the obtained compound of formula (RD-02) is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.80 (2H, s), 7.45 (4H, m), 6.80 (8H, m), 6.60 (8H, m), 6.53 (4H, dd) , 5.99 (4H, dd), 5.70 (4H, dd), 4.89 (8H, s), 4.05 (8H, t), 3.85

Then, the texture of the compound of the above formula (RD-02) was observed with a polarizing microscope and the phase transition temperature was measured. As a result, the nematic phase of the crystal phase changed at about 195 ° C as the temperature increased, and an isotropic liquid crystal phase appeared at about 210 ° C. In this way, it has been confirmed that the compound of formula (RD-02) forms a nematic phase at a temperature range of about 195 ° C to 210 ° C.

(2) Production of optically anisotropic film (phase difference film)

A retardation film was prepared under the same conditions and the same procedure as in Example 1 except that the compound of the formula (RD-02) was used, and Δn values thereof were determined.

As a result,? N (450 nm),? N (550 nm) and? N (650 nm) were measured to be 0.096, 0.101 and 0.103, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.95 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.02 and it was confirmed that the conditions according to the above formulas I and II were satisfied.

Example  3

(1) Synthesis of Polymerizable Liquid Crystal Compound

A polymerizable liquid crystal compound (RD-03) was synthesized according to the following Reaction Scheme 3.

[Reaction Scheme 3]

First, a compound of the formula (a-1) (about 7.5 g) [Polym. Adv. Technol. 2006. 17, 444], 4,4'-diethynylbiphenyl (about 1.5 g) of the formula (b-2) [Chem. (About 122 mg) and triethylamine (100 ml) and dimethylformamide (50 ml) were added to a solution of bis (triphenylphosphine) palladium (II) dichloride (about 0.47 g) Dissolved in a mixed solution. The solution was stirred at about 70 ° C for 5 hours and cooled to precipitate crystals, and the precipitate was collected by filtration, washed with methanol and dried to give the compound of formula (c-2) (about 6 g).

The compound of formula (c-1) (about 5 g) and the compound of formula (d-2) (about 3.3 g) [Chem. Commun., 2010, 46, 5536] was dissolved in toluene (200 ml), and a Dean-Stark trap was installed, and the mixture was heated under reflux for 12 hours. After the solution was cooled to room temperature, a large amount of methanol was added to the reaction solution to precipitate a solid. The solvent was then removed by filtration, and vacuum drying gave the compound of formula (e-4) (about 8.5 g).

The compound of the above formula (e-4) (about 8 g) was dissolved in dimethylacetamide (90 ml), cooled to 0 캜, acryloyl chloride (about 6.7 g) was added dropwise for 30 minutes, And stirred for 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous solution of sodium chloride. The organic portion was collected, and after chemical drying, the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain a compound of the formula (RD-03) (about 7.5 g).

The NMR spectrum of the obtained compound of formula (RD-03) is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.88 (2H, s), 7.49 (4H, m), 7.40 (4H, m), 6.89 (8H, m), 6.60 (8H, m) , 6.39 (4H, dd), 6.05 (4H, dd), 5.95 (4H, dd), 4.81 (8H, s), 4.24 1.50 (32H, m), 1.20 (32H, m)

The structure of the compound of the above formula (RD-03) was observed with a polarizing microscope and the phase transition temperature was measured. As a result, the temperature was changed from about 201 ° C to a nematic phase of the crystal phase, and when the temperature exceeded about 220 ° C, an isotropic liquid crystal phase appeared. In this way, it has been confirmed that the compound of formula (RD-03) forms a nematic phase at a temperature range of about 201 ° C to 220 ° C.

(2) Production of optically anisotropic film (phase difference film)

A retardation film was prepared in the same manner as in Example 1 except that the compound of the above formula (RD-03) was used, and Δn values thereof were determined.

As a result, Δn (450 nm), Δn (550 nm), and Δn (650 nm) were measured to be 0.078, 0.090, and 0.094, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.87 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.04 and it was confirmed that the conditions according to the above formulas I and II were satisfied.

Example  4

(1) Synthesis of Polymerizable Liquid Crystal Compound

A polymerizable liquid crystal compound (RD-04) was synthesized according to Reaction Scheme 4 below.

[Reaction Scheme 4]

First, a compound of the formula (a-1) (about 7.5 g) [Polym. Adv. Technol. (About 1.5 g), bis (triphenylphosphine) palladium (II) dichloride (about 0.47 g) of the formula (b-1), and copper iodide 122 mg) was dissolved in a mixed solution of triethylamine (100 ml) and dimethylformamide (50 ml). The solution was stirred at about 70 < 0 > C for 5 hours and cooled to precipitate crystals. The precipitate was collected by filtration, washed with methanol and dried to give the compound of formula (c-1) (about 6.5 g).

The compound of the above formula (c-1) (about 6 g) and the compound of the formula (d-3) (about 3.3 g) [J. Chem. Soc, PT1, 1985, 9, 1829] was dissolved in toluene (200 ml), and a Dean-Stark trap was installed. The mixture was heated at reflux for 12 hours. After the solution was cooled to room temperature, a large amount of methanol was added to the reaction solution to precipitate a solid. Thereafter, the solvent was removed by filtration, and a compound of the formula (e-5) (about 6.9 g) was obtained through vacuum drying.

Then, the compound of the above formula (e-5) (about 6 g) was dissolved in dimethylacetamide (90 ml), cooled to 0 ° C, acryloyl chloride (about 6.7 g) was added dropwise for 30 minutes, And stirred for 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous solution of sodium chloride. The organic portion was collected, and after chemical drying, the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain the compound of formula (RD-04) (about 5.1 g).

The NMR spectrum of the obtained compound of formula (RD-04) is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.93 (2H, s), 7.42 (8H, m), 6.65 (8H, m), 6.43 (4H, dd), 6.05 (4H, dd) , 5.80 (4H, dd), 4.89 (8H, s), 4.57 (8H, t), 4.20

Then, the structure of the compound of the above formula (RD-04) was observed with a polarizing microscope and the phase transition temperature was measured. As a result, the temperature was changed from about 192 ° C to a nematic phase of the crystal phase, and when the temperature exceeded about 220 ° C, an isotropic liquid crystal phase appeared. In this way, it has been confirmed that the compound of formula (RD-04) forms a nematic phase at a temperature range of about 192 ° C to 220 ° C.

(2) Production of optically anisotropic film (phase difference film)

A retardation film was prepared under the same conditions and procedures as in Example 1 except that the compound of the above formula (RD-04) was used, and Δn values thereof were determined.

As a result, Δn (450 nm), Δn (550 nm), and Δn (650 nm) were measured to be 0.080, 0.088, and 0.096, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.91 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.03 and it was confirmed that the conditions according to the above formula I and II were satisfied.

Example  5

(1) Synthesis of Polymerizable Liquid Crystal Compound

A polymerizable liquid crystal compound (RD-05) was synthesized according to Reaction Scheme 5 below.

[Reaction Scheme 5]

First, a compound of the formula (a-1) (about 7.5 g) [Polym. Adv. Technol. (About 1.5 g), bis (triphenylphosphine) palladium (II) dichloride (about 0.47 g) of the formula (b-1), and copper iodide 122 mg) was dissolved in a mixed solution of triethylamine (100 ml) and dimethylformamide (50 ml). The solution was stirred at about 70 < 0 > C for 5 hours and cooled to precipitate crystals. The precipitate was collected by filtration, washed with methanol and dried to give the compound of formula (c-1) (about 6.5 g).

4'-hydroxy-4-biphenyl carbonate (about 3.3 g) of the compound of the formula (c-1) (about 6 g) and the compound of the formula (d-4) [Chem. Commun., 2010, 46, 5536] was dissolved in toluene (200 ml), and a Dean-Stark trap was installed, and the mixture was heated under reflux for 12 hours. After the solution was cooled to room temperature, a large amount of methanol was added to the reaction solution to precipitate a solid. Thereafter, the solvent was removed by filtration, and a compound of the formula (e-6) (about 6.4 g) was obtained through vacuum drying.

The compound of the above formula (e-6) (about 6 g) was dissolved in dimethylacetamide (90 ml), cooled to 0 캜, acryloyl chloride (about 6.7 g) was added dropwise for 30 minutes, And stirred for 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous solution of sodium chloride. The organic portion was collected, and after chemical drying, the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain a compound of formula (RD-05) (about 5.4 g).

The NMR spectrum of the obtained compound of formula (RD-05) is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.93 (2H, s), 7.60 (20H, m), 7.02 (8H, m), 6.88 (8H, m), 6.33 (4H, dd) , 6.08 (4H, dd), 5.85 (4H, dd), 4.80 (8H, s), 4.19

Then, the texture of the compound of the above formula (RD-05) was observed with a polarizing microscope and the phase transition temperature was measured. As a result, the temperature was changed from about 255 ° C to the nematic phase of the crystal phase, and when the temperature exceeded about 281 ° C, an isotropic liquid crystal phase appeared. In this way, it has been confirmed that the compound of formula (RD-05) forms a nematic phase at a temperature range of about 255 ° C to 281 ° C.

(2) Production of optically anisotropic film (phase difference film)

A retardation film was prepared in the same manner as in Example 1 except that the compound of the above formula (RD-05) was used, and Δn values thereof were determined.

As a result, Δn (450 nm), Δn (550 nm), and Δn (650 nm) were measured to be 0.108, 0.114, and 0.116, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.95 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.02 and it was confirmed that the conditions according to the above formulas I and II were satisfied.

Example  6

(1) Synthesis of Polymerizable Liquid Crystal Compound

A polymerizable liquid crystal compound (RD-06) was synthesized according to the following Reaction Scheme 6.

[Reaction Scheme 6]

First, a compound of the formula (a-1) (about 7.5 g) [Polym. Adv. Technol. 2006. 17, 444], 4,4'-diethynylbiphenyl (about 1.5 g) of the formula (b-2) [Chem. (About 122 mg) and triethylamine (100 ml) and dimethylformamide (50 ml) were added to a solution of bis (triphenylphosphine) palladium (II) dichloride (about 0.47 g) Dissolved in a mixed solution. The solution was stirred at about 70 ° C for 5 hours and cooled to precipitate crystals, and the precipitate was collected by filtration, washed with methanol and dried to give the compound of formula (c-2) (about 6 g).

4'-hydroxy-4-biphenyl carbonate (about 3.3 g) of the compound of the formula (c-2) (about 5 g) and the compound of the formula (d-4) [Chem. Commun., 2010, 46, 5536] was dissolved in toluene (200 ml), and a Dean-Stark trap was installed, and the mixture was heated under reflux for 12 hours. After the solution was cooled to room temperature, a large amount of methanol was added to the reaction solution to precipitate a solid. Thereafter, the solvent was removed by filtration, and a compound of the formula (e-7) (about 5.3 g) was obtained through vacuum drying.

Then, the compound of the above formula (e-7) (about 5 g) was dissolved in dimethylacetamide (90 ml), cooled to 0 ° C, acryloyl chloride (about 6.7 g) was added dropwise for 30 minutes, And stirred for 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous solution of sodium chloride. The organic portion was collected, and after chemical drying, the solvent was distilled off under reduced pressure. The obtained product was purified by column chromatography to obtain a compound of formula (RD-06) (about 4.5 g).

The NMR spectrum of the obtained compound of formula (RD-06) is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 8.81 (2H, s), 7.52 (4H, m), 7.44 (20H, m), 7.00 (8H, m), 6.78 (8H, m) (8H, d), 6.81 (4H, dd), 5.81 (4H, dd), 4.82 (8H, s), 4.15

The structure of the compound of formula (RD-06) was observed with a polarizing microscope and the phase transition temperature was measured. As a result, an isotropic liquid crystal phase appeared when the temperature exceeded about 285 ° C. In this way, it has been confirmed that the compound of formula (RD-06) forms a nematic phase in the temperature range of about 260 ° C to 285 ° C.

(2) Production of optically anisotropic film (phase difference film)

A retardation film was prepared in the same manner as in Example 1 except that the compound of the above formula (RD-06) was used, and Δn values thereof were determined.

As a result,? N (450 nm),? N (550 nm) and? N (650 nm) were measured to be 0.069, 0.077 and 0.081, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.89 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.05 and it was confirmed that the conditions according to the above formulas I and II were satisfied.

Reference example  One

(Preparation of optical anisotropic body)

A retardation film was produced under the same conditions and in the same manner as in Example 1 except that the polymerizable liquid crystal compound (RM 257, manufacturer: XI'AN RUILIAN MODERN Co., Ltd) represented by the following formula (10) n values were obtained.

As a result, Δn (450 nm), Δn (550 nm), and Δn (650 nm) were measured at 0.132, 0.115, and 0.106, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 1.18 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 0.92, Respectively.

[Chemical formula 10]

Example  7

Except that the compound of the formula (RD-01) according to Example 1 and the compound of the formula (RD-07) according to the Example 6 were mixed in a weight ratio of 1: 1, A retardation film was prepared, and the value of DELTA n was obtained therefrom.

As a result,? N (450 nm),? N (550 nm) and? N (650 nm) were measured as 0.081, 0.091 and 0.096, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.89 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.05 and it was confirmed that the conditions according to the above formulas I and II were satisfied.

Reference example  2

Except that the compound of the formula (RD-01) according to Example 1 and the compound of the formula 10 (RM 257) according to the Reference Example 1 were mixed at a weight ratio of 1: 1, And a value of DELTA n was obtained therefrom.

As a result,? N (450 nm),? N (550 nm) and? N (650 nm) were measured as 0.102, 0.100 and 0.097, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) is 1.02 and the value of DELTA n (650 nm) / DELTA n (550 nm) is 0.97, Respectively.

Example  8

The same conditions and methods as in Example 1 were used except that the compound of the formula (RD-01) according to Example 1 and the compound of the formula 10 (RM 257) according to the Reference Example 1 were mixed at a weight ratio of 2: And a value of DELTA n was obtained therefrom.

As a result,? N (450 nm),? N (550 nm) and? N (650 nm) were measured as 0.088, 0.091 and 0.092, respectively. Therefore, the value of DELTA n (450 nm) / DELTA n (550 nm) was 0.97 and the value of DELTA n (650 nm) / DELTA n (550 nm) was 1.01 and it was confirmed that the conditions according to the above formula I and II were satisfied.

Claims (11)

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

In Formula 1,
A ¹ to A ⁸ are each O;
D ¹ to D ⁴ are each N;
E ¹ to E ^4, and J ¹ to J ⁴ are each independently _{-CH 2 -, - (CH 2} ) 2 -, - (CH 2) 3, - (CH 2) 4 -, - (CH 2) 5 - _{, - (CH 2) 6 -} , -Ph-, -Ph (CH 3) -, -Ph-CH 2 -, -Ph- (CH 2) 2 -, -Ph- (CH 2) 3 -, - ( Ph) ₂ -, - (Ph) ₂ -CH ₂ - or - (Ph) ₂ - (CH ₂ ) ₂ -, Ph is a phenyl group;
G ¹ to G ⁴ each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR-, -NR- _{-NR-CO-NR-, -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 -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - -, or -C? C-, each R is independently hydrogen or an alkyl group having 1 to 10 carbon atoms;
L ¹ to L ⁴ each independently represent an acrylate group, a methacrylate group or an epoxy group;
M is -C≡C-, -C≡CC≡C-, -C≡C-Ph-C≡C-, -C≡C-Ph-Ph-C≡C-, or -C≡C-Ph- C? C-Ph-C? C-, and Ph is a phenyl group;
m, n and p each independently represent an integer of 1 to 5;
delete delete delete delete A polymerizable liquid crystal composition comprising a compound according to claim 1.
The method according to claim 6,
A polymerization initiator and a solvent.
An optically anisotropic composition comprising a cured product or polymer of a polymerizable liquid crystal compound represented by formula (1) according to claim 1.
9. The method of claim 8,
An optically anisotropic composition comprising a cured product or polymer wherein at least a part of terminal polymerizable groups of the polymerizable liquid crystal compound of Formula 1 is addition polymerized or crosslinked.
9. The method of claim 8,
An optically anisotropic material satisfying the following formulas I and II:
(Formula I)
DELTA n _{(450 nm )} / DELTA n _{(550 nm )} < 1.0
(Formula II)
? N _{(650 nm )} /? N _{(550 nm )} > 1.0
In the above formula (I) and formula (II),? N (?) Means the specific refractive index at the wavelength? Within the liquid crystal phase.
An optical element for a liquid crystal display device comprising the optically anisotropic element according to claim 8.