WO2014003416A1

WO2014003416A1 - Polymerizable liquid crystal compound, and liquid crystal composition and optically anisotropic body comprising same

Info

Publication number: WO2014003416A1
Application number: PCT/KR2013/005608
Authority: WO
Inventors: 서경창; 전성호; 최대승; 홍미라; 장형빈
Original assignee: 주식회사 엘지화학
Priority date: 2012-06-28
Filing date: 2013-06-25
Publication date: 2014-01-03

Abstract

The present invention relates to a polymerizable liquid crystal compound, and to a liquid crystal composition and optically anisotropic body comprising same. The polymerizable liquid crystal compound according to the present invention makes it possible to produce an optically anisotropic body that not only has a high birefractive index but also has outstanding orientation properties during coating and has outstanding optical properties despite being thin.

Description

【Specification】

[Name of invention]

Polymerizable liquid crystal compound, liquid crystal composition and optically anisotropic body comprising the same

The present invention relates to a polymerizable liquid crystal compound, a liquid crystal composition comprising the same and an optically anisotropic body.

[Background Art] ^"

A phase retarder is a type of optical device that changes the polarization state of light passing through it, also called a wave plate. When the electromagnetic wave passes through the phase retarder, the polarization direction (field vector direction) is the sum of two components (normal and extraordinary) 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. Since it changes, the polarization direction after passing is different.

One of the major issues related to the production of optical films used in phase retarders and the like in recent years is the production of high performance films at low cost. This is because when a liquid crystal compound having a high birefringence is used in manufacturing the optical film, it is possible to realize a phase difference value even with a small amount of the liquid crystal compound. Moreover, when using such a liquid crystal compound, a thinner thin film can be manufactured.

To this end, studies to obtain a liquid crystal compound having a high birefringence have been actively conducted. However, when the liquid crystal compound is coated on a film, there is a limit to the practical application in the industry due to the problem of the orientation of the film. [Contents of the Invention]

[Problem to solve]

Accordingly, the present invention is to provide a polymerizable liquid crystal compound having high birefringence and excellent in orientation during coating.

Moreover, this invention is providing the polymerizable liquid crystal composition containing the said compound.

Moreover, this invention is providing the optically anisotropic body containing the polymer of the said polymeric liquid crystal composition. [Measures of problem]

According to the present invention, a polymerizable liquid crystal compound 0 represented by Formula 1 is provided:

In Chemical Formula 1,

A is an alkyl group having 1 to 10 carbon atoms;

D ¹ , D ² , G ¹ and G ² are each independently a single bond or a divalent linking group, wherein at least one of D ¹ , D ² , G ¹ and G ² is an imine group;

E ¹ and E ² are each independently a benzene ring or a naphthalene ring, and at least one of E ¹ and E ² is a naphthalene ring;

J ¹ and J ² are each independently an alkylene group of 1 to 10 carbohydrates;

L ¹ and L ² are each independently hydrogen or a polymerizable group.

In addition, according to another embodiment of the present invention, a polymerizable liquid crystal composition including the compound represented by Chemical Formula 1 is provided.

In addition, according to another embodiment of the present invention, an optically anisotropic body including a cured product or a polymer of the polymerizable liquid crystal compound is provided.

[Effects of the Invention]

The polymerizable liquid crystal compound according to the present invention not only has a high birefringence but also has excellent orientation in coating, thereby enabling the production of an optically anisotropic body having a thin thickness and excellent optical properties.

[Brief Description of Drawings]

1 and 2 are photographs taken by the method of Test Example 2 to confirm the degree of light leakage with respect to the retardation film containing a compound according to an embodiment and a comparative example of the present invention.

[Specific contents to carry out invention]

Hereinafter, a polymerizable liquid crystal compound according to embodiments of the present invention, The liquid crystal composition and optically anisotropic body to be included will be described.

Prior to this, the terminology is for the purpose of describing particular embodiments only and is not intended to limit the invention, unless expressly stated throughout this specification.

As used herein, the singular forms “a,” “an,” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.

In addition, the meaning of "included" as used in the specification specifies a specific characteristic, region, integer, step, operation, element or component, excluding the addition of other specific characteristics, region, integer, step, operation, element, or component. It is not meant to be.

Meanwhile, the 'polymerizable liquid crystal compound' is a liquid crystal compound having a polymerizable functional group, and after aligning a liquid crystal composition containing at least one polymerizable liquid crystal compound in a liquid crystal state, irradiating active energy rays such as ultraviolet rays in that state. In this case, a polymer obtained by immobilizing the alignment structure of the liquid crystal molecules can be obtained. The polymer obtained in this way has anisotropy of physical properties such as refractive index, dielectric constant, magnetization rate, elasticity rate and thermal expansion rate, and thus can be used as an optical anisotropic body such as retardation film, polarizing plate, polarizing prism, brightness enhancement film, coating material of optical fiber and the like. Do. In addition to the anisotropy of such a polymer, physical properties such as transparency, strength, applicability, solubility, crystallinity, and heat resistance are also important. The inventors of the present invention have repeatedly studied the liquid crystal compound, polymerizable liquid crystal compound having a chemical structure as shown in the following formula (1), in particular having a central benzene ring in which an alkyl substituent is introduced, at least one imine linking group and naphthalene ring linking group in the main chain At the same time, the polymerizable liquid crystal compound not only has a high birefringence but also has excellent orientation in coating, enabling the manufacture of an optically anisotropic body having a thin thickness and excellent optical properties, thereby completing the present invention.

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

[Formula 1]

In Chemical Formula l,

A is an alkyl group having 1 to 10 carbon atoms;

L ¹ and L ² are each independently a hydrogen group or a polymerizable group. The polymerizable liquid crystal compound represented by Chemical Formula 1 may have a structure in which at least one imine linking group is introduced into a compound in which a condensed ring is introduced into mesogen, thereby exhibiting high birefringence and excellent orientation in coating. have.

According to the present invention, in Chemical Formula 1, A is a substituent bonded to the central benzene ring of the compound, and the polymerizable liquid crystal compound may have more excellent orientation, and may reduce light leakage of the retardation film manufactured using the same. . According to one embodiment, A may be an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

In addition, in Formula 1, D ¹ , D ² , G ^1, and G ² may be each independently a single bond or a divalent linking group. Here, the divalent linking group is -CH = N-, -0-, -S-, -CO-, -C00-, -0C0-, -0-C00-, -C0-NR-, -NR- C0-, -NR-C0-NR-,-0CH _2- , -CH ₂ O-, -SCH-, -CH ₂ S-, -CF ₂ 0-, _0CF _2- , _CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -,-(C¾) ₃ -,-(CH ₂ ) _4- , -CF ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CF _2- , -C = C- Or -C≡C-, wherein R can be each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. In particular, according to the present invention, at least one of the D ¹ , D ² , G ¹ and G ² It may be an imine group (_CH = N-), and preferably, the D ¹ and D ² , or G ¹ and G ² may each be an imine group. The polymerizable liquid crystal compound of the exemplary embodiment may include ¾ NMR spectrum having at least one peak at δ of 8.0 ppm to 8.5 ppm as including at least one imine group.

In addition, in Formula 1, Ε ¹ and Ε ² are each independently a benzene ring or a naphthalene ring, at least one of Ε ¹ and Ε ² may be a naphthalene ring, and preferably, the Ε ¹ and Ε ² are each naphthalene ring. Can be.

That is, the polymerizable liquid crystal compound of the embodiment has a central benzene ring in which an alkyl substituent is introduced, and in particular, has a structure in which at least one imine linking group and a naphthalene ring linking group are simultaneously introduced into the main chain. Accordingly, the polymerizable liquid crystal compound of the above embodiment can exhibit not only higher birefringence by synergism by these substituents and linking groups, but also excellent orientation when coating the composition including the same, and the thickness is thin. It is possible to manufacture an optically anisotropic body having excellent optical properties.

Meanwhile, in Formula 1, J ¹ and J ² may each independently be an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 2 to 9 carbon atoms, and more preferably an alkylene group having 3 to 6 carbon atoms. Can be.

In addition, in Formula 1, L ¹ and L ² may be each independently hydrogen or a polymerizable group, wherein the 'polymerizable group' refers to any functional group capable of crosslinking or polymerizing such as an unsaturated bond or a (meth) acrylate group. It can be defined as. According to the present invention, L1 and L2 may each independently be a hydrogen group, an acrylate group, a methacrylate group, an epoxy group, or the like. Specific examples of the polymerizable liquid crystal compound represented by Chemical Formula 1 include the following Chemical Formulas 2a and 2b. In Formulas 2a and 2b, R ¹ and R ² may be each independently an alkyl group having 1 to 10 carbon atoms, and n may be an integer of 1 to 10, respectively. However, the polymerizable liquid crystal compound of the present invention is not limited only to the following exemplary compounds.

[Formula 2a]

Meanwhile, the polymerizable liquid crystal compound represented by Chemical Formula 1 may be prepared by applying a known reaction, which will be described in detail in the Examples of the present specification. On the other hand, according to another embodiment of the present invention, a polymerizable liquid crystal composition comprising the compound represented by Formula 1 is provided.

The composition according to the present invention includes a compound represented by Formula 1, which is a polymerizable liquid crystal monomer, and the compound represented by Formula 1, alone or in combination of two or more, may be homopolymerized or copolymerized.

The composition may further include any liquid crystal compound in addition to the compound represented by Chemical Formula 1, and the arbitrary liquid crystal compound may be polymerizable or non-polymerizable. Here, as said arbitrary liquid crystal compound, the liquid crystal compound which has an ethylenically unsaturated bond, the compound which has an optical active group, a rod-like liquid crystal compound, etc. are mentioned.

At this time, the arbitrary liquid crystal compounds may be mixed in an appropriate amount according to their structure, preferably, so that the compound represented by the formula (1) according to the present invention is included in more than 60% by weight of the total monomer weight, It is more advantageous in terms of achieving one object.

In addition, a solvent, a polymerization initiator, a storage stabilizer, a liquid crystal alignment aid, a dye, and a pigment may be further added to the polymerizable liquid crystal composition, and the additive may be conventional components in the art to which the present invention pertains. Therefore, the configuration is not particularly limited. On the other hand, according to another embodiment of the present invention, an optically anisotropic body including a cured product or polymer of the polymerizable liquid crystal compound of Formula 1 is provided. The optically anisotropic body may include a cured product or polymer in which at least a part of the terminal polymerizable group of the polymerizable liquid crystal compound of Chemical Formula 1 is additionally polymerized or crosslinked.

In particular, the optically anisotropic body according to the present invention includes a cured product or a polymerized body of the above-described polymerizable liquid crystal compound, and exhibits a high retardation value, but may have no light leakage phenomenon or minimize it. In addition, the optically anisotropic body according to the present invention can be manufactured in a simpler process with a thin thickness as compared with the previous laminated optical anisotropic body. On the other hand, the optically anisotropic body may be prepared by coating and drying the polymerizable liquid crystal composition on a support, orienting the liquid crystal compound, and then polymerizing by irradiating ultraviolet rays or the like.

Here, the support is not particularly limited, but preferably, a glass plate, a polyetherine terephthalate film, or a cellulose-based film spout may be used. In addition, as a method of applying the polymerizable liquid crystal composition to a support, a known method may be applied without particular limitation. For example, a coating method, a spin coating method, a bar coating method, a spray coating method, or the like may be applied. In addition, as the method for orienting the polymerizable liquid crystal composition, a known method such as a method of rubbing the formed composition layer or applying a magnetic field or an electric field to the formed composition layer may be applied.

And, the thickness of the optically anisotropic body can be adjusted according to the use, preferably can be adjusted in the range of 0.01 to 100 kHz.

Such optically anisotropic medium of the present ^invention, used as an optical element such as a phase difference film, an optical compensating plate of the liquid crystal display device, an alignment film, a polarizing plate, a viewing angle enlargement plate, a reflecting film, color filters, holographic elements, optical polarization prism, an optical head Can be. Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples according to the present invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

Scheme 1: Example 1 to Example 10

Example 1: Synthesis of Compound 3-a

2-met hyl benzene- l, ⁴ _di amine which is the compound l_a in Scheme 1 [Journal of Chemical Research, 2005, 2, 123] After about 8 g of ethane was dissolved in about 80 ml, it was heated to about 90 ^° C. Here, a solution of about 40 g of 6-hydroxy-2-naphthaldehyde as a compound 2 dissolved in about 150 ml of ethane was added dropwise, followed by stirring under reflux for about 8 hours. The reaction mixture was cooled to room temperature to obtain a solid product, which was filtered through ethane and dried in vacuo to yield about 24 g of compound 3-a (R ^ methyl).

Example 2: Synthesis of Compound 3-b

About 31 g of Compound 3-b (R ^ ethyl) was obtained by the same method and conditions as in Example 1, except that 2-ethylbenzene-l, 4-diamineol, which was Compound 1-b, was used instead of Compound 1-a. Example 3: Synthesis of Compound 4-a

About 10 g of compound 3-a according to Example 1, about 6.6 g of 3-chloropropanol, and about 13 g of potassium carbonate were dissolved in acetone, followed by stirring under reflux for about 24 hours. The reaction mixture was cooled to room temperature, filtered to remove solids and distilled under reduced pressure. Then, about 11.5 g of Compound 4-a (R ^ methyl, η = 3) was obtained through column chromatography.

Example 4: Synthesis of Compound 4-b

About 10.4 g of Compound 4-b (R ^ methyl, η = 6) was obtained by the same method and conditions as in Example 3, except that 6-chloronucleol was used instead of 3-chloropropanol.

Example 5: Synthesis of Compound 4-c

About 12 g of Compound 4-c (R ^ ethyl, n = 3) was obtained by the same method and conditions as in Example 3, except that Compound 3-b according to Example 2 was used instead of Compound 3-a.

Example 6: Synthesis of Compound 4-d

About 12.5 g of Compound 4- in the same manner and conditions as in Example 3, except that Compound 3-b according to Example 2 was used instead of Compound 3-a and 6-chloronucleoanol was used instead of 3-chloropropanol d (R ^ ethyl, η = 6) was obtained. Example 7: Synthesis of Compound RM-It

About 10 g of Compound 4-a according to Example 3 was dissolved in about 100 ml of dimethylacetamide, and then cooled to about 0 ^° C. About 3.3 g of acryloyl chloride was added dropwise over 30 minutes, and stirred at room temperature for about 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous sodium chloride solution. The organic portion was collected therefrom, chemically dried, and then distilled under reduced pressure to remove the solvent. The obtained product was column chromatograph purified to obtain about llg of compound RM-01 (R ^ methyl, n = 3).

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

¾ NMR (CDC1 ₃₎ standard TMS) δ (ppm): 8.39 (2H, s), 8.28 (2H, s),

7.96 (2H, d), 7.84 (2H, m), 7.60 (2H, m), 7.10 (7H, m), 6.41 (2H, dd), 6.03 (2H, dd), 5.82 (2H, dd), 4.12 (4H, m), 4.03 (4H, m), 2.36 (3H, s), 1.98 (2H, m)

And the structure of the compound RM-01 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, the temperature was changed to a nematic phase of the crystalline phase at about 167 ^° C., the isotropic liquid crystal phase appeared when it exceeds about 181 ^° C. In this way, it was confirmed that compound RM- forms a nematic phase in the temperature range of about 167 ^° C to 181 ^° C.

Example 8: Synthesis of Compound RM-02

About 10.2 g of Compound RM-02 (R ^ methyl, n = 6) was obtained by the same method and conditions as in Example 7, except that Compound 4-b according to Example 4 was used instead of Compound 4-a.

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

XH NMR (CDC1 ₃₎ Standard TMS) δ (ppm): 8.38 (2H, s), 8.26 (2H, s), 7.91 (2H, d), 7.81 (2H, m), 7.62 (2H, m), 7.16 (7H, m), 6.44 (2H, dd) ^' , 6.05 (2H, dd), 5.81 (2H, dd), 4.14 (4H, m), 4.06 (4H, m), 2.34 (3H, s), 1.71 (4H, m), 1.57 (4H, m), 1.29 (8H, m)

And the structure of the compound RM-02 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-02 forms a nematic phase in the temperature range of about 170 ^° C to 185 ^° C. Example 9: Synthesis of Compound RM-03

About 11.9 g of Compound RM-03 (R ^{1 =} ethyl, n = 3) was obtained by the same method and conditions as in Example 7, except that Compound 4-c according to Example 5 was used instead of Compound 4-a.

The NMR spectrum of the compound RM-03 is as follows.

¾ NMR (CDCls, Standard TMS) δ (ppm): 8.40 (2H, s), 8.27 (2H, s), 7.91 (2H, d), 7.82 (2H, m), 7.57 (2H, m), 7.11 (7H, m), 6.42 (2H, dd), 6.03 (2H, dd), 5.84 (2H, dd), 4.11 (4H, m), 4.00 (4H, m), 2.53 (2H, s), 1.94 ( 2H, m), 1.24 (3H, m)

And the structure of the compound RM-03 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-03 forms a nematic phase in the temperature range of about 148 ^° C to 161 ^° C.

Example 10 Synthesis of Compound RM-04

About 10.3 g of Compound RM-04 (R ^ ethyl, n = 6) was obtained by the same method and conditions as in Example 7, except that Compound 4-d according to Example 6 was used instead of Compound 4-a.

The NMR spectrum of the compound RM-04 is as follows.

¾ NMR (CDC1 ₃ , standard TMS) δ (ppm): 8.41 (2H, s), 8.29 (2H, s), 7.95 (2H, d), 7.84 (2H, m), 7.62 (2H, m), 7.16 (7H, m), 6.43 (2H, dd), 6.01 (2H, dd), 5.81 (2H, dd), 4.14 (4H, m), 4.04 (4H, m), 2.58 (3H, s), 1.71 (4H, m), 1.54 (4H, m), 1.22 (8H, ra)

Then, the structure of compound RM-04 was observed with a polarizing microscope and the phase transition temperature was measured. As a result, it was confirmed that compound RM-04 forms a nematic phase in the temperature range of about 178 ^° C to 189 ^° C.

Scheme 2: Example 11-Example 20

Example 11: Synthesis of Compound 6-a

Compound 5-a in Scheme 2 [Journal of Medicinal Chemi stry, 2008, 51, 17, 5176] After about 8g was dissolved in about 80ml of ethanol and heated to about 9C C. Here, a solution of about 40 g of 6-hydroxy-2-naphthaldehyde as a compound 2 dissolved in about 150 ml of ethane was added dropwise, followed by stirring under reflux for about 8 hours. The reaction mixture was cooled to room temperature to obtain a solid product, which was filtered through ethane and dried in vacuo to give about 22 g of compound 6-a (n = 3).

Example 12: Synthesis of Compound 6-b

About 27 g of Compound 6-b (n = 6) by the same method and conditions as in Example 11, except that Compound 5-b [Organic & Biomolecular Chemistry, 2008, 6, 7, 1176] was used instead of Compound 5-a. Got. Example 13: Synthesis of Compound 8-a

2-methylterephthalic acid, which is about 10 g of compound 6-a (n = 3) according to Example 11, compound 7_a (R ² = methyl) [Chem. COmm. , 2011, 47, 18, 5244] About 2.9 g, and about 6.5 g of EDC (N- (3-dimethylaminopropyl) -N'-ethyl carbodi imide hydrochloride) were dissolved in dichloromethane and cooled to about 0 ^° C. About 0.4 g of dimethylaminopyridine and about 8 g of diisopropylethylamine were added thereto, followed by stirring for about 3 hours. The reaction solution was distilled with dichloromethane, washed with 1N hydrochloric acid and brine, and chemically dried. Then, a semi-ungmul was obtained through filtration and distillation under reduced pressure, which was purified by column chromatography to obtain about 10.5 g of Compound 8-a (R ² = methyl, η = 3).

Example 14 Synthesis of Compound 8-b

About 12.4 g of Compound 8-b (R ² = methyl, η = was the same method and conditions as in Example 13 except that Compound 6-b (n = 6) according to Example 12 was used instead of Compound 6-a 6) was obtained.

Example 15 Synthesis of Compound 8-c

About 11.5 g of Compound 8-c (R ² = ethyl, n = 3) was obtained by the same method and conditions as in Example 13, except that 2-ethylterephthalic acid, which was Compound 7-b, was used instead of Compound 7-a.

Example 16: Synthesis of Compound 8-c The same method and conditions as in Example 13, except that Compound 6-b (n = 6) according to Example 12 was used instead of Compound 6-a, and 2-ethylterephthalic acid, which was Compound b, was used instead of Compound 7-a. About 10.4 g of Compound 8-d (R ² = ethyl, η = 6) was obtained. Example 17: Synthesis of Compound R¾H) 5

About 10 g of compound 8-a according to Example 13 and about 0.4 _g of PPTS (pyridinium paraluenesulfonate) were dissolved in tetrahydrofuran and stirred at reflux for about 2 hours. Then, the solvent was removed by distillation under reduced pressure, diluted with dichloromethane, and washed with brine. The organic layer obtained therefrom was chemically dried and distilled under reduced pressure to obtain a white solid compound.

The white solid compound was dissolved in about 100 ml of dimethylacetamide, and then cooled to about 0 ^° C. About 3.3 g of acryloyl chloride was added dropwise over 30 minutes, and stirred at room temperature for about 2 hours. The semi-aqueous solution was diluted with diethyl ether and washed with an aqueous sodium chloride solution. The organic portion was collected therefrom, chemically dried, and then distilled under reduced pressure to remove the solvent. The obtained product was purified by column chromatography to obtain about 9. Compound R-05 (R ² = methyl, n = 3).

The NMR spectrum of the compound RM-05 is as follows.

¾ NMR (CDC1 ₃ , standard TMS) δ (ppm): 8.26 (2H, s), 8.12 (5H, m), 7.91 (2H, m), 7.77 (2H, m), 7.64 (2H, m) ₍ 6.99 (4H, m), 6.41 (2H, dd), 6.02 (2H, dd), 5.83 (2H, dd), 4.11 (4H, m), 3.53 (4H, m), 2.35 (3H, s), 1.91 (2H, m)

And the structure of the compound RM-05 was observed by the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-05 forms a nematic phase in the temperature range of about 153 ^° C to 177 ^° C.

Example 18 Synthesis of Compound R-06

Compound RM-06 of about lO.lg in the same methods and conditions as in Example 17, except that Compound 8-b according to Example 14 was used instead of Compound 8-a (R ² = methyl ₍ n = 6) was obtained.

The NMR spectrum of the compound RM-06 is as follows.

¾ NMR (CDCls, Standard TMS) δ (ppm): 8.23 (2H, s), 8.10 (5H, m), 7.89 (2H, m), 7.74 (2H, m), 7.61 (2H, m) ₎ 6.94 (4H, m), 6.38 (2H, dd), 6.00 (2H, dd), 5.80 (2H, dd), 4.12 (4H, m), 3.53 (4H, m), 2.34 (3H, s), 1.61 ( 8H, m), 1.29 (8H, m) ^''

And the structure of the compound RM-06 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-06 forms a nematic phase in the temperature range of about 150 ° C to 184 ^° C.

Example 19: Synthesis of Compound R-07

About 9.8 g of Compound RM-07 (R ² = ethyl, n = 3) was obtained by the same method and conditions as in Example 17, except that Compound 8-c according to Example 15 was used instead of Compound 8-a.

The NMR spectrum of the compound RM-07 is as follows.

¾ NMR (CDC1 ₃₎ standard TMS) δ (ppm): 8.25 (2H, s), 8.10 (5H, m),

7.91 (2H, m), 7.74 (2H, ra), 7.61 (2H, m), 7.01 (4H, m), 6.42 (2H, dd), 6.01 (2H, dd), 5.86 (2H, dd), 4.14 (4H, m), 3.51 (4H, m), 2.54 (5H, s), 1.94 (2H, m), 1.21 (3H, m)

And the structure of the compound RM-07 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-07 forms a nematic phase in the temperature range of about 164 ^° C to 180 ^° C.

Example 20 Synthesis of Compound R-08

About ll.Og of compound RM-08 (R ² = ethyl, n = 6) was obtained by the same method and conditions as in Example 17, except that Compound 8-d according to Example 16 was used instead of Compound 8-a. .

The NMR spectrum of the compound RM-08 is as follows.

¾ NMR (CDCls, Standard TMS) δ (ppm): 8.26 (2H, s), 8.12 (5H, m), 7.89 (2H, m), 7.75 (2H, m), 7.64 (2H, m), 6.95 (4H, m), 6.38 (2H, dd), 6.01 (2H, dd), 5.81 (2H, dd), 4.15 (4H, m), 3.53 (4H, m), 2.53 (2H, s), 1.62 ( 8H, m), 1.28 (8H, m), 1.20 (3H, m) And the structure of the compound RM-08 was observed with a polarizing microscope and the phase transition temperature was measured. As a result, it was confirmed that compound RM-08 forms a nematic phase in the temperature range of about 178 ^° C to 202 ^° C.

[Scheme 3: Comparative Example 1 to Comparative Example 6]

Comparative Example 1: Synthesis of Compound 10-a

About 100 g of methyl 6-hydroxy-2-naphthoate, compound 9 of Scheme 3, about 94 g of 3-chloropropanol, and about 182 g of potassium carbonate were added to acetone. After melting, the mixture was stirred under reflux for about 24 hours. The reaction mixture was cooled to room temperature, filtered to remove solids and distilled under reduced pressure. Then, about 13¾ of compound 10-a (n = 3) was obtained by column chromatography.

Comparative Example 2: Synthesis of Compound 10-b

About 110 g of Compound 10-b (n = 6) was obtained by the same method and conditions as in Comparative Example 1, except that 6-chloronucleol was used instead of 3-chloropropanol. Comparative Example 3: Synthesis of Compound 11-a

About 120 g of compound 10-a according to Comparative Example 1 and about 21 g of PPTS (pyridinium paraluenesulfonate) were dissolved in dichloromethane, and then cooled to about 0 ^° C. About 42 g of 3,4-dihydro_2H-pyran was dissolved in dichloromethane and added dropwise thereto, followed by stirring for about 12 hours. Then, the semi-aqueous solution was washed with brine and chemically dried, followed by distillation under reduced pressure to obtain about 145 g of compound 11-a (n = 3).

Comparative Example 4: Synthesis of Compound 11-b

About 110 g of Compound 11-b (n = 6) was obtained by the same method and conditions as the Comparative Example 3, except that Compound 10-b according to Comparative Example 2 was used instead of Compound 10-a. Comparative Example 5: Synthesis of Compound 12-a

About 140 g of Compound 11-a according to Comparative Example 3 was dissolved in methane, and sodium hydroxide (2M, 300 ml) was added thereto, and the mixture was stirred under reflux for about 2 hours and distilled under reduced pressure. After dissolving the reaction in water and dichloromethane, the pH was adjusted to 5 using 3M hydrochloric acid. The organic layer was separated, chemically dried, distilled under reduced pressure, and washed with nucleic acid to obtain compound 12-a (n = 3) as a white solid.

Comparative Example 6: Synthesis of Compound 12-b

About 89 g of Compound 12-b by the same methods and conditions as Comparative Example 5, except that Compound 11-b according to Comparative Example 4 was used instead of Compound 11-a (n = 6) was obtained.

Scheme 4: Comparative Example 7 Comparative Example

Comparative Example 7: Synthesis of Compound 14-a Compound 12-a according to Comparative Example 5, about 12. lg, about 13 g of hydroquinone as compound 13, and about 7.2 g of EDC (N- (3-dimethylaminopropyl) -N'-ethylcarbodi imide hydrochloride) were dissolved in dichloromethane. Cooled to 0 ^° C. About 0.9 g of dimethylaminopyridine and about 9 g of diisopropylethylamine were added thereto, followed by stirring for about 3 hours. The reaction solution was diluted with dichloromethane, washed with 1N hydrochloric acid and brine, and chemically dried. Then, a semi-ungmul was obtained through filtration and distillation under reduced pressure, which was purified by column chromatography to obtain about 10.5 g of Compound 14-a (n = 3).

Comparative Example 8: Synthesis of Compound 14-b

About 11.5 g of Compound 14-b (n = 6) was obtained by the same method and conditions as the Comparative Example 7, except that Compound 12-b according to Comparative Example 6 was used instead of Compound 12-a. Comparative Example 9: Synthesis of Compound RM-09

About 10 g of compound 14-a according to Comparative Example 7 and about 0.4 g of PPTS (pyridinium paraluenesulfonate) were dissolved in tetrahydrofuran and stirred at reflux for about 2 hours. Then, the solvent was removed by distillation under reduced pressure, diluted with dichloromethane, and washed with brine. The organic layer obtained therefrom was chemically dried and distilled under reduced pressure to obtain a white solid compound.

The white solid compound was dissolved in about 90 ml of dimethylacetamide, and then cooled to about 0 ^° C. About 7 g of acryloyl chloride was added dropwise over 30 minutes, and stirred at room temperature for about 2 hours. The reaction solution was diluted with diethyl ether and washed with an aqueous sodium chloride solution. The organic portion was collected therefrom, chemically dried, and then distilled under reduced pressure to remove the solvent. The obtained product was column chromatograph purified to give about 12.0 g of compound RM-09 (n = 3).

The NMR spectrum of the compound RM-09 is as follows.

¾ CD (CDCl _3l standard TMS) δ (ppm): 8.52 (2H, s), 8.20 (2H, d), 7.75 (2H, d), 7.60 (2H, d), 7.22 (4H, s), 7.02 (4H, m), 6.44 (2H, dd), 6.09 (2H, dd), 5.90 (2H, dd), 4.04 (4H, ra), 3.95 (4H, m), 1.99 (4H, m)

And the structure of the compound RM-09 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-09 forms a nematic phase in the temperature range of about 190 ^° C to 205 ^° C.

Comparative Example 10 Synthesis of Compound R-10

About ll.lg Compound RM-10 (n = 6) was obtained by the same method and conditions as the Comparative Example 9, except that Compound 14-b according to Comparative Example 8 was used instead of Compound 14-a.

The NMR spectrum of the compound RM-10 is as follows.

¾ NMR (CDCls, standard TMS) δ (ppm): 8.50 (2H, s), 8.19 (2H, d),

7.73 (2H, d), 7.62 (2H, d), 7.24 (4H, s), 7.00 (4H, m), 6.45 (2H, dd), 6.07 (2H, dd), 5.91 (2H, dd), 4.14 (4H, m), 4.04 (4H, m), 1.75 (4H, m), 1.51 (4H, m), 1.29 (8H, m)

And the structure of the compound RM-10 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-10 forms a nematic phase in the temperature range of about 201 ^° C to 212 ^° C.

Scheme 5: Comparative Example 11 to Comparative Example 13

Comparative Example n: Synthesis of Compound 16

About 22 g of Compound 16 was obtained by the same method and conditions as in Example 1, except that 4-hydr oxybenza ldehyde, which was Compound 15, was used instead of Compound 2.

Comparative Example 12: Synthesis of Compound 17

About 15.3 g of Compound 17 was prepared by the same method and conditions as in Example 3, except that Compound 16 according to Comparative Example 11 was used instead of Compound 3-a. Got it.

Comparative Example 13: Synthesis of Compound R-11

Example 7 About 12 g of Compound RM-11 was obtained by the same method and conditions as in Example 7, except that Compound 17 according to Comparative Example 12 was used instead of Compound 4-a.

The NMR spectrum of the compound RM-11 is as follows.

¾ C (CDC1 ₃ , standard TMS) δ (ppm): 8.39 (2H, s), 7.85 (4H, m), 7.30 (2H, m), 7.06 (4H, m), 6.46 (lH, d), 6.27 (2H, dd), 6.05 (2H, dd), 5.59 (2H, dd), 4.20 (8H, m), 2.36 (3H, s), 2.10 (4H, m)

And the structure of the compound RM-11 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-11 forms a nematic phase in the temperature range of about 103 ^° C to 132 ^° C.

Scheme 6: Comparative Example 14-Comparative Example 15

Comparative Example 14 Synthesis with Compound 19

About 15 g of Compound 19 was obtained by the same method and conditions as in Comparative Example 7, except that 2-methylbenzene-l, 4-di, which was Compound 18, was used instead of Compound 13.

Comparative Example 15 Synthesis of Compound RM-12

About 9 g of Compound RM-12 was obtained by the same method and conditions as the Comparative Example 9, except that Compound 19 according to Comparative Example 14 was used instead of Compound 14-a. Got it.

The NMR spectrum of the compound RM-12 is as follows.

^: H NMR (CDCI3, Standard TMS) δ (ppm): 8.64 (2H, s), 8.32 (2H, d), 7.92 (4H, d), 7.88 (4H, d), 7.42 (3H, m), 6.43 (2H, dd), 6.04 (2H, dd), 5.92 (2H, dd), 4.16 (4H, m), 4.03 (4H, m), 2.15 (3H, s), 1.75 (4H, m), 1.49 (4H, m), 1.29 (8H, m)

And the structure of the compound RM-12 was observed with the polarizing microscope, and the phase transition temperature was measured. As a result, it was confirmed that compound RM-12 forms a nematic phase in the silver range of about 198 ^° C to 210 ^° C. Preparation Examples 1 to 8 (Manufacture of Retardation Film)

Based on 100 parts by weight of the total composition, 25 parts by weight of the compound RM-01, 5 parts by weight of Irgacure 907 (manufactured by Ciba-Geigy, Switzerland) as a photoinitiator, and a polymerizable liquid crystal composition including a balance of CPO (cyclopentanone) was prepared. The liquid crystal composition was coated on a norbornene-based photoalignment material-coated COP (cycloolefin polymer) film by a coating method, and then dried ^at about 90 ^° C. for 2 minutes to align the liquid crystal compound. Thereafter, the film was irradiated with non-polarized UV light having a high pressure mercury lamp of 200 mW / ciif as a light source to fix the alignment state of the liquid crystal to prepare a retardation film.

In the same manner as described above, a composition including any one of compounds RM-02 to RM-08 instead of compound RM-01 was prepared, and retardation films were prepared, respectively.

Comparative Production Examples 1 to 4 (Production of Phase Difference Film)

Retardation films were prepared in the same manner as in Preparation Examples 1 to 8, except that Compound RM-09, RM-10, RM-11, or RM-12 according to Comparative Examples was used instead of Compound RM-01.

Reference Example

A retardation film was manufactured in the same manner as in Preparation Examples 1 to 8, except that the polymerizable liquid crystal compound (RM 257, manufactured by ΧΓΑΝ RUILIAN MODERN Co., Ltd) was used instead of the compound RM-01. [Formula 10]

Test Example 1

For each retardation film according to Production Examples 1 to 8, Comparative Production Examples 1 to 4, and Reference Example, the quantitative phase difference value was measured using Axoscan (manufactured by Axomatrix). In this case, the thicknesses were measured independently, Δη values were obtained from the obtained values, and the results are shown in Table 1 below.

Test Example 2

Between the polarizing plates arranged in an orthogonal state, each retardation film according to Production Examples 1 to 8, Comparative Production Examples 1-4 and Reference Example was placed, and then light leakage was obtained by using ECLIPSE LV100P0L (manufactured by Nikon). It was confirmed. The photographing results are shown in FIGS. 1 and 2 for each compound.

Table 1

As can be seen from Table 1, as can be seen from Table 1, in the case of a retardation film containing the compound RM— 09, RM-10, or RM-12, the orientation of the compound in the manufacturing process The irregular birefringence could not be measured. In addition, the compound RM-11 including the imine linkage group in the main chain but not the naphthalene ring had good orientation, but the birefringence was similar to that of the compound RM257. In contrast, it was confirmed that the retardation film including the compounds RM-01 to RM-08 according to Preparation Examples 1 to 8 has a relatively higher birefringence than the conventional film.

Furthermore, as can be seen from FIGS. 1 and 2, the retardation film including the compounds RM-01 to RM-08 according to Preparation Examples 1 to 8 has a light leakage phenomenon compared to the films of Comparative Preparation Examples 1 to 4 and Reference Examples. It was confirmed that almost did not appear either.

Claims

[Patent Claims]

[Claim 1]

A polymerizable liquid crystal compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

A is an alkyl group having 1 to 10 carbon atoms;

D ¹ , D ² , G ¹ and G ² are each independently a single bond or a divalent linking group, wherein at least one of D ¹ , D ² ᅳ G ¹ and G ² is an imine group;

L ¹ and L ² are each independently hydrogen or a polymerizable group. [Claim 2]

The method of claim 1,

A polymerizable liquid crystal compound having a ¾ NMR spectrum having at least one peak at δ of 8.0 ppm to 8.5 ppm. Claim 3-The method of claim 1,

D ¹ , D ² , G ¹ and G ² are each independently a single bond, -CH = N-, -0-, -S-, -CO—, -C00-, -0C0-, -0-C00- , -C0-NR-, -NR-C0-, -NR-C0-NR-, -0CH _2- , -CH ₂ 0-, -SCH-, -C¾S-, -CF ₂ 0-, -0CF _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 is independently hydrogen or an alkyl group having 1 to 10 carbon atoms;

At least one of D ¹ , D ² , G ^1, and G ² is an imine group (—CH = N—) Liquid crystal compound.

[Claim 4]

The method of claim 1,

The polymerizable liquid crystal compound wherein E ¹ and E ² are each a naphthalene ring.

[Claim 5]

The method of claim 1,

The L ¹ and L ² are each independently a hydrogen group, an acrylate group, a methacrylate group or an epoxy group.

[Claim 6]

A polymerizable liquid crystal composition comprising the compound according to claim 1. [Claim 7]

The method of claim 6,

A polymerizable liquid crystal composition further comprising a polymerization initiator and a solvent. [Claim 8]

An optically anisotropic body comprising a cured product or a polymer of the polymerizable liquid crystal compound according to claim 1.

[Claim 9]

The method of claim 8,

An optically anisotropic body comprising a cured product or a polymer in which at least a part of the terminal polymerizable group of the polymerizable liquid crystal compound of Formula 1 is polymerized or crosslinked.

[Claim 10]

An optical element for a liquid crystal display device comprising the optical barrier according to claim 8.