KR20240121066A - T-shaped negative dispersion reactive mesogen compound containing imine group - Google Patents

Abstract

The present invention relates to a photoreactive mesogen compound including an imine and a method for producing the same. The photoreactive mesogen compound of the present invention has an increase in birefringence as the wavelength increases, and thus a polymerizable composition containing the same can be usefully used as an antireflection film material by film formation.

Description

T-shaped negative dispersion reactive mesogen compound containing imine group {T-shaped negative dispersion reactive mesogen compound containing imine group}

The present invention relates to a reactive mesogenic compound having reverse wavelength dispersion including imine and a method for producing the same.

When light passes through a medium with optical anisotropy, a difference in the speed of light, that is, a difference in the refractive index, occurs between the long axis direction of the molecule and the direction perpendicular to it. This is called the birefringence phenomenon. Due to this birefringence phenomenon, if the thickness of the medium through which the light passes is d and the wavelength of the incident light is λ, a phase difference of 2πΔnd/λ occurs after passing through the medium. By controlling the birefringence and thickness of the medium, the polarization of the incident light can be changed, and such a device is called a phase retardation plate or phase difference film. When linearly polarized light is incident, if the phase difference value of the phase retardation plate is π, the polarization of the transmitted light becomes linearly polarized perpendicular to the incident light, and such a phase retardation plate is called a half-wave phase retardation plate. Also, if the phase difference of the medium is π/2, the incident linearly polarized light becomes circularly polarized, and such a phase retardation plate is called a quarter-wave phase retardation plate.

Phase retardation plates that can change the shape and direction of polarization are used in displays as polarizing plates, anti-reflection films, and image quality improvement films. OLED displays have a problem in that external light is reflected due to the high proportion of metal electrodes, which significantly reduces the visibility of the screen. To solve this problem, phase retardation plates are applied as anti-reflection films.

The quarter-wave phase retardation plate used in LCD compensation film or OLED display antireflection film is manufactured by stretching a polymer film or coating a polymeric liquid crystal material. In the case of the currently commercialized antireflection film for OLED, a compensation film is used in which a half-wave retarder and a quarter-wave retarder are sequentially laminated on a linear polarizing film.

In order to maximize the performance of an optical film for a display, the phase retardation plate must have the same phase retardation value in all visible light ranges. However, most media with optical anisotropy have positive dispersion characteristics in which the birefringence decreases as the wavelength increases. As a result, the phase retardation value decreases as the wavelength increases, and in the case of a compensation film designed for a specific wavelength, the phase retardation value is different in other wavelength ranges, limiting the optical effect. Therefore, in order to maximize the performance of a compensation film, a material with negative dispersion characteristics in which the birefringence increases as the wavelength increases is required (Non-patent literature, Jiyong Hwang, et al, Optics Express Vol, 24, No. 17).

In general, the refractive index of a material is related to the absorption wavelength of light. The decrease in refractive index occurs greatly near the maximum absorption wavelength, and the decrease in refractive index becomes smaller as it moves away from the maximum absorption wavelength. Therefore, if the molecule is designed to have the maximum absorption wavelength at a long wavelength in the long axis direction and the maximum absorption wavelength at a shorter wavelength in the direction perpendicular to the long axis, the decrease in refractive index in the long axis direction decreases rapidly with wavelength, and in the direction perpendicular to the long axis, the decrease in refractive index appears gradual as the wavelength increases, resulting in the expression of wavelength reverse dispersion characteristics in which the birefringence value increases as the wavelength increases.

Accordingly, the inventors of the present invention designed and synthesized a compound for changing the birefringence of a liquid crystal according to the wavelength, and discovered that the T-type reactive mesogen compound according to the present invention exhibited reverse wavelength dispersion when mixed with a host liquid crystal having forward wavelength dispersion, thereby completing the present invention.

One object of the present invention is to provide a novel reactive mesogen compound.

Another object of the present invention is to provide a method for producing the reactive mesogenic compound.

Another object of the present invention is to provide a negative dispersion type polymerizable composition comprising the reactive mesogenic compound.

Another object of the present invention is to provide a phase difference film manufactured from the composition.

Another object of the present invention is to provide a liquid crystal film manufactured from the composition.

Another object of the present invention is to provide an antireflection film manufactured from the above-mentioned phase difference film.

To achieve the above purpose,

The present invention provides a reactive mesogen compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

R is C _6-18 aryl or 5-14 atoms, unsubstituted or substituted with Y. Heteroaryl, where Y is C _6-18 aryl or 5-14 atoms substituted through vinylene. is heteroaryl;

A is one or more combinations selected from C=O, O, S, NH;

B is C _6-18 arylene;

C is L ² -C _1-20 alkylene, wherein L ² is one or more combinations selected from C=O, O, S, NH;

X is a photocrosslinkable functional group containing one or more radically polymerizable double bonds in the molecule.

On the other hand, as shown in the following reaction scheme 1,

A method comprising the step of producing a compound represented by chemical formula 1 by reacting a compound represented by chemical formula 2 with chemical formula 3.

A method for producing a compound represented by chemical formula 1 is provided.

[Reaction Formula 1]

In the above reaction formula 1,

The positions of R, A, B, C, X, and -A-B-C-X are as defined in the chemical formula 1 above.

In another aspect, a negative dispersion polymerizable composition comprising the reactive mesogenic compound is provided.

In another aspect, a phase difference film manufactured from the above composition is provided.

In another aspect, an antireflection film manufactured from a phase difference film is provided.

The photoreactive mesogenic compound of the present invention has an increase in birefringence as the wavelength increases, and thus a polymerizable composition containing the same can be usefully used as an antireflection film material by film formation.

Figure 1 is a graph showing the absorbance according to wavelength of a compound according to an embodiment of the present invention.
Figure 2 is a drawing showing the orientation characteristics of a compound according to an embodiment of the present invention.
Figure 3 is a graph evaluating the wavelength dispersion of a phase retardation film using a compound according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

Meanwhile, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to a person having average knowledge in the relevant technical field.

Furthermore, reference throughout the specification to an element “including” means that, unless otherwise specifically stated, it may include other elements, rather than excluding other elements.

The term "aryl" or "arylene", unless otherwise specified, includes a monovalent or divalent residue of an aromatic hydrocarbon. For example, "C _6-14 arylene" includes a divalent radical of an aromatic hydrocarbon ring compound having from 6 to 14 carbons. The aromatic hydrocarbon ring compound may be a condensed two or more, for example 2-3, benzene rings. Examples thereof include phenyl, naphthyl, and anthracenyl.

The term "alkyl" or "alkylene", unless otherwise specified, includes a monovalent or divalent residue of a straight or branched chain saturated hydrocarbon. For example, "C _1-6 alkylene" means an alkyl having a skeleton of from 1 to 6 carbons. Specifically, C _1-6 alkylene can include methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, t-butylene, n-pentylene, i-pentylene, t-pentylene, sec-pentylene, neopentylene, hexylene, and the like.

The term "heteroaryl", or "heteroarylene", unless otherwise specified, includes an aromatic monovalent or divalent radical of a single ring or two or three fused rings having one or more aromatic rings containing 1, 2 or 3 ring-forming heteroatoms selected from N, O or S.

One aspect of the present invention is:

A reactive mesogen compound represented by the following chemical formula 1 is provided.

[Chemical Formula 1]

In the above chemical formula 1,

R is C _6-18 aryl or 5-14 atoms, unsubstituted or substituted with Y. Heteroaryl, where Y is C _6-18 aryl or 5-14 atoms substituted through vinylene. is heteroaryl;

A is one or more combinations selected from C=O, O, S, NH;

B is C _6-18 arylene;

C is L ² -C _1-20 alkylene, wherein L ² is one or more combinations selected from C=O, O, S, NH;

X is a photocrosslinkable functional group containing one or more radically polymerizable double bonds in the molecule.

In the above chemical formula 1, another example is,

The above R is C _6-14 aryl or 5-14 atoms It may be a C _6-14 aryl substituent linked via heteroaryl or vinylene.

In the above chemical formula 1, another example is,

The above A is It could be.

In the above chemical formula 1, another example is,

The above C is L ² -C _1-15 alkylene, wherein L ² can be O.

In the above chemical formula 1, another example is,

The above X is It could be.

In the above chemical formula 1, another example is,

wherein R is phenyl, naphthyl, anthracenyl, dibenzothiophenyl, or phenylethenylphenyl;

The two -A-B-C-X are bonded to each other in the para position in the benzene ring;

A is and;

B is phenylene;

C is OC _1-10 alkylene;

X is It could be.

As a concrete example,

The compound according to the above chemical formula 1 can be selected from the following.

;

;

;

;

;

;

; and

.

In another aspect of the present invention,

As shown in the following reaction scheme 1,

A method comprising the step of producing a compound represented by chemical formula 1 by reacting a compound represented by chemical formula 2 with chemical formula 3.

A method for producing a compound represented by chemical formula 1 is provided.

[Reaction Formula 1]

In the above reaction formula 1,

The positions of R, A, B, C, X, and -A-B-C-X are as defined in the chemical formula 1 above.

Hereinafter, the manufacturing method of the above reaction scheme 1 is described in detail.

The above step is a step for producing a compound represented by chemical formula 1 that includes an imine by reacting an amine and an aldehyde. The reaction generally proceeds through nucleophilic addition, but any method for synthesizing an imine is not limited thereto and may be carried out according to methods known in the art.

The above manufacturing method is not limited to one embodiment of the present invention presented as an example, and can be performed by modifying the solvent, reactant, temperature conditions, etc. under general organic chemical knowledge.

In another aspect of the present invention,

A reverse wavelength dispersion polymerizable composition comprising the above reactive mesogenic compound is provided.

In another aspect of the present invention,

A phase difference film manufactured from the above composition is provided.

In another aspect of the present invention,

A liquid crystal film manufactured from the above composition is provided.

In another aspect of the present invention,

An anti-reflection film manufactured from the above phase difference film is provided.

Hereinafter, the present invention will be described in detail through examples and experimental examples.

However, the examples and experimental examples described below are only specific examples of one aspect of the present invention, and the present invention is not limited thereto.

< Example 1 > (E)-2-(( Phenylimino ) methyl )-1,4- Phenylene Bis(4-((6-(acryloyloxane) Preparation of (C)hexyl)oxy)benzoate

Step 1: Preparation of 2-formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate

및 질소 분위기 하에서 트리에틸아민 (14.1 mL, 101.36 mmol), 메탄설포닐 클로라이드 (3.4 mL, 43.44 mmol)를 천천히 적가한 후 3시간 동안 교반하였다. 50

로 온도를 높인 후, 2,5-다이하이드록시벤즈알데하이드 (2 g, 14.48 mmol)를 소량의 테트라하이드로퓨란에 녹여서 적가한 후 24시간 동안 교반하였다. 반응 혼합물에 과량의 증류수를 부어 반응을 종료하고 초산 에틸로 추출하여, 용매를 모두 증발 시킨 후 얻은 고체를 에탄올로 세척하여 상아색의 고체(8.54 g, 86%)를 수득하였다. Dissolve 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid (9.31 g, 31.86 mmol) in 60 mL of tetrahydrofuran in a reaction vessel, 0

And under a nitrogen atmosphere, triethylamine (14.1 mL, 101.36 mmol) and methanesulfonyl chloride (3.4 mL, 43.44 mmol) were slowly added dropwise and stirred for 3 hours. 50

After increasing the temperature, 2,5-dihydroxybenzaldehyde (2 g, 14.48 mmol) dissolved in a small amount of tetrahydrofuran was added dropwise, and stirred for 24 hours. An excessive amount of distilled water was added to the reaction mixture to terminate the reaction, and the mixture was extracted with ethyl acetate. After evaporating all the solvent, the obtained solid was washed with ethanol to obtain an ivory-colored solid (8.54 g, 86%).

1H NMR (Chloroform-d, 500 MHz): δ (ppm) 10.21 (s, 1H), 8.27 - 8.10 (m, 4H), 7.79 (d, J=2.9 Hz, 1H), 7.53 (dd, J=8.8 , 2.9 Hz, 1H), 7.39 (d, J=8.8 Hz, 1H), 6.99 (t, J=9.0 Hz, 4H), 6.40 (dd, J=17.4, 1.5 Hz, 2H), 6.13 (dd, J =17.3, 10.4 Hz, 2H), 5.82 (dd, J=10.5, 1.5 Hz, 2H), 4.19 (t, J=6.6 Hz, 4H), 4.07 (td, J=6.3, 4.2 Hz, 4H), 1.85 (h, J=5.7, 4.4 Hz, 4H), 1.73 (p, J=6.9 Hz, 4H), 1.59 - 1.43 (m, 8H)

Step 2: Preparation of (E)-2-((phenylimino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1.1 g, 1.6 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. Aniline (0.15 mL, 1.6 mmol) was slowly added dropwise at 65°C, and the mixture was stirred for 24 hours. After cooling to room temperature and filtering, the solvent was removed, and the obtained solid was washed with hexane and ethanol to obtain 1.22 g (93%) of an ivory solid.

1H NMR (Chloroform-d, 500 MHz): δ (ppm) 8.57 (s, 1H), 8.16 (dd, J=8.7, 5.9 Hz, 4H), 8.10 (d, J=2.8 Hz, 1H), 7.40 ( dd, J=8.8, 2.8 Hz, 1H), 7.33 (t, J=7.9 Hz, 3H), 7.19 (t, J=7.4 Hz, 1H), 7.13 - 7.08 (m, 2H), 7.00 - 6.95 (m , 4H), 6.40 (dt, J=17.4, 1.7 Hz, 2H), 6.13 (ddd, J=17.3, 10.4, 2.3 Hz, 2H), 5.82 (dt, J=10.5, 1.8 Hz, 2H), 4.19 (td, J=6.7, 2.6 Hz, 4H), 4.06 (td, J=6.4, 2.7 Hz, 4H), 1.84 (td, J =8.9, 4.6 Hz, 4H), 1.73 (pd, J=6.7, 2.8 Hz, 4H), 1.58 - 1.45 (m, 8H)

< Example 2 > (E)-2-((naphthalene-1- Illimino ) methyl )-1,4- Phenylene Bis (4-((6-( Acryloyloxy ) Manufacture of ) Hexyl ) Oxy ) Benzoate

Step 1: Preparation of (E)-2-((naphthalen-1-ylamino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. At 65°C, 1-naphthylamine (0.25 g, 1.75 mmol) dissolved in a small amount of ethanol was slowly added dropwise, and the mixture was stirred for 24 hours. After cooling to room temperature and filtering, the solvent was removed, and the obtained solid was washed with hexane and ethanol to obtain 0.671 g (57%) of solid.

1H NMR (Methylene Chloride-d2, 500 MHz): δ (ppm) 8.70 (s, 1H), 8.26 (dd, J=8.2, 1.4 Hz, 1H), 8.23 (d, J=2.8 Hz, 1H), 8.21 - 8.15 (m, 4H), 7.84 - 7.81 (m, 1H), 7.70 (d, J=8.3 Hz, 1H), 7.52 - 7.36 (m, 5H), 7.04 - 7.00 (m, 2H), 7.00 - 6.96 (m, 3H), 6.36 (ddd, J=17.3, 4.8, 1.5 Hz, 2H), 6.12 (ddd, J=17.3, 10.4, 5.3 Hz, 2H), 5.80 (ddd, J=10.4, 4.9, 1.6 Hz, 2H), 4.15 (q, J=6.8 Hz, 4H), 4.06 (dt, J=18.4, 6.5 Hz, 4H), 1.83 (ddd, J=14.4, 8.0, 6.2 Hz, 4H), 1.76 - 1.67 (m, 4H), 1.58 - 1.42 (m, 8H)

< Example 3 > (E)-2-((naphthalene-2- Illimino ) methyl )-1,4- Phenylene Bis (4-((6-( Acryloyloxy ) Manufacture of ) Hexyl ) Oxy ) Benzoate

Step 1: Preparation of (E)-2-((naphthalen-2-ylimino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. At 65°C, 2-naphthylamine (0.25 g, 1.75 mmol) dissolved in a small amount of ethanol was slowly added dropwise, and the mixture was stirred for 24 hours. After cooling to room temperature and filtering, the solvent was removed, and the obtained solid was washed with hexane and ethanol to obtain 0.879 g (74%) of a solid.

1H NMR (Methylene Chloride-d2, 400 MHz): δ (ppm) 8.77 (s, 1H), 8.23 (dd, J=8.7, 6.1 Hz, 4H), 8.17 (d, J=2.8 Hz, 1H), 7.85 (t, J=7.6 Hz, 3H), 7.55 (d, J=2.1 Hz, 1H), 7.53 - 7.43 (m, 3H), 7.43 - 7.36 (m, 2H), 7.12 - 7.00 (m, 4H), 6.40 (ddd, J=17.4, 4.0, 1.6 Hz, 2H), 6.16 (ddd, J=17.3, 10.4, 4.6 Hz, 2H), 5.85 (ddd, J=10.4, 4.6, 1.6 Hz, 2H), 4.20 (td, J=6.6, 4.9 Hz, 4H), 4.11 (q, J=6.9 Hz, 4H), 1.88 (h, J =6.7 Hz, 4H), 1.76 (h, J=6.5 Hz, 4H), 1.64 - 1.44 (m, 8H)

< Example 4 > (E)-2-((anthracene-1- Illimino ) methyl )-1,4- Phenylene Bis (4-((6-( Acryloyloxy ) Manufacture of ) Hexyl ) Oxy ) Benzoate

Step 1: Preparation of (E)-2-((anthracen-1-ylimino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. 1-Aminoanthracene (0.34 g, 1.75 mmol) dissolved in a small amount of ethanol at 65°C was slowly added dropwise, and the mixture was stirred for 4 hours. After cooling to room temperature, the formed precipitate was filtered and washed with ethanol to obtain 1.0742 g (86%) of a yellow solid.

1H NMR (Methylene Chloride-d2, 500 MHz): δ (ppm) 8.82 (s, 1H), 8.77 (s, 1H), 8.41 (s, 1H), 8.32 (d, J=2.9 Hz, 1H), 8.24 - 8.15 (m, 4H), 8.05 - 7.98 (m, 2H), 7.87 (d, J=8.6 Hz, 1H), 7.50 - 7.43 (m, 3H), 7.39 (dd, J=8.7, 7.0 Hz, 2H) ), 7.06 - 7.01 (m, 2H), 6.98 - 6.92 (m, 3H), 6.36 (ddd, J=17.3, 6.7, 1.5 Hz, 2H), 6.11 (ddd, J=17.5, 10.4, 7.5 Hz, 2H), 5.80 (ddd, J=10.4, 6.6, 1.5 Hz, 2H), 4.15 (dt, J=11.1, 6.7 Hz, 4H) ), 4.08 (t, J=6.5 Hz, 2H), 4.02 (t, J=6.5 Hz, 2H), 1.91 - 1.77 (m, 4H), 1.71 (dp, J=14.2, 6.8 Hz, 4H), 1.59 - 1.38 (m, 8H)

< Example 5 > (E)-2-((anthracene-2- Illimino ) methyl )-1,4- Phenylene Bis (4-((6-( ah Preparation of Chryloyloxy) Hexyloxy) Benzoate

Step 1: Preparation of (E)-2-((anthracen-2-ylimino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy) benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. At 65°C, 2-aminoanthracene (0.34 g, 1.75 mmol) dissolved in a small amount of ethanol was slowly added dropwise, and the mixture was stirred for 4 hours. After cooling to room temperature, the formed precipitate was filtered and washed with ethanol to obtain 0.9910 g (79%) of an ivory solid.

1H NMR (Methylene Chloride-d2, 500 MHz): δ (ppm) 8.80 (s, 1H), 8.41 - 8.36 (m, 2H), 8.23 - 8.16 (m, 4H), 8.15 (d, J=2.8 Hz, 1H), 8.01 - 7.94 (m, 3H), 7.66 (dd, J=2.0, 0.9 Hz, 1H), 7.51 - 7.33 (m, 5H), 7.05 - 6.99 (m, 4H), 6.36 (ddd, J= 17.3, 9.1, 1.6 Hz, 2H), 6.11 (dt, J=17.3, 10.2 Hz, 2H), 5.80 (td, J=10.4, 1.5 Hz, 2H), 4.15 (dt, J=11.0, 6.6 Hz, 4H), 4.07 (dt, J=11.8, 6.4 Hz, 4H), 1.83 (ddd, J=14.4, 12.1 , 6.6 Hz, 4H), 1.76 - 1.65 (m, 4H), 1.58 - 1.41 (m, 8H)

< Example 6 > (E)-2-((anthracene-9- Illimino ) methyl )-1,4- Phenylene Bis (4-((6-( Acryloyloxy ) Manufacture of ) Hexyl ) Oxy ) Benzoate

Step 1: Preparation of (E)-2-((anthracene-9-ylimino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. 9-Aminoanthracene (0.34 g, 1.75 mmol) dissolved in a small amount of ethanol at 65°C was slowly added dropwise, and the mixture was stirred for 6 hours. After cooling to room temperature and filtering, the solvent was removed, and the obtained solid was washed with ethanol to obtain 0.9738 g (78%) of a solid.

1H NMR (Methylene Chloride-d2, 500 MHz): δ (ppm) 8.79 (m, 1H), 8.40 - 8.36 (m, 2H), 8.25 - 8.18 (m, 4H), 8.15 (d, J=2.8 Hz, 1H), 8.02 - 7.94 (m, 3H), 7.66 (dd, J=2.0, 0.9 Hz, 1H), 7.51 - 7.33 (m, 5H), 7.05 - 6.99 (m, 4H), 6.36 (ddd, J= 17.3, 9.1, 1.6 Hz, 2H), 6.11 (dt, J=17.3, 10.2 Hz, 2H), 5.80 (td, J=10.4, 1.5 Hz, 2H), 4.15 (dt, J=11.0, 6.6 Hz, 4H), 4.07 (dt, J=11.8, 6.4 Hz, 4H), 1.83 (ddd, J=14.4, 12.1 , 6.6 Hz, 4H), 1.76 - 1.65 (m, 4H), 1.58 - 1.41 (m, 8H)

< Example 7 > 2-((E)-((4-((E)- Styryl )phenyl)imino) methyl )-1,4- Phenylene Bis Preparation of (4-((6-(acryloyloxy)hexyl)oxy)benzoate)

Step 1: Preparation of 2-((E)-((4-((E)-styryl)phenyl)imino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was increased to 65°C. At 65°C, 4-aminostilbene (0.34 g, 1.75 mmol) dissolved in a small amount of ethanol was slowly added dropwise, and the mixture was stirred for 6 hours. After cooling to room temperature and filtering, the solvent was removed, and the obtained solid was washed with ethanol to obtain 1.1227 g (89%) of solid.

1H NMR (Methylene Chloride-d2, 500 MHz): δ (ppm) 8.64 (s, 1H), 8.21 - 8.14 (m, 4H), 8.08 (d, J=2.8 Hz, 1H), 7.54 - 7.48 (m, 4H), 7.40 (dd, J=8.8, 2.8 Hz, 1H), 7.37 - 7.32 (m, 3H), 7.27 - 7.23 (m, 1H), 7.17 - 7.13 (m, 2H), 7.10 (d, J= 1.8 Hz, 2H), 7.03 - 6.99 (m, 4H), 6.36 (ddd, J=17.4, 4.6, 1.5 Hz, 2H), 6.12 (ddd, J=17.3, 10.4, 4.8 Hz, 2H), 5.80 (ddd, J=10.4, 5.8, 1.5 Hz, 2H), 4.16 (td, J=6.7, 3.7 Hz, 4H), 4.07 (td, J=6.5, 2.3 Hz, 4H), 1.84 (pd, J=6.5, 3.1 Hz, 4H), 1.72 (pd, J=6.7, 3.8 Hz, 4H), 1.58 - 1.43 (m, 8H)

< Example 8 > (E)-2-(( Dibenzo[b,d]cyophene -2- Illimino ) methyl )-1,4- Phenylene Bis Preparation of (4-((6-(acryloyloxy)hexyl)oxy)benzoate)

Step 1: Preparation of (E)-2-((dibenzo[b,d]thiophene-2-ylimino)methyl)-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate)

2-Formyl-1,4-phenylene bis(4-((6-(acryloyloxy)hexyl)oxy)benzoate (1 g, 1.46 mmol) was dissolved in 20 mL of ethanol in a reaction vessel, and the temperature was raised to 65°C. 2-Aminodibenzoside phene (0.32 g, 1.60 mmol) dissolved in a small amount of ethanol was slowly added dropwise, and the mixture was stirred for 6 hours. After cooling to room temperature and filtering, the solvent was removed, and the obtained solid was washed with ethanol to obtain 0.324 g (26%) of solid.

1H NMR (Methylene Chloride-d2, 500 MHz): δ (ppm) 8.76 (s, 1H), 8.23 - 8.15 (m, 4H), 8.12 (d, J=2.8 Hz, 1H), 8.10 - 8.07 (m, 1H), 7.88 (d, J=2.0 Hz, 1H), 7.87 - 7.84 (m, 1H), 7.81 (d, J=8.4 Hz, 1H), 7.48 - 7.44 (m, 2H), 7.42 (dd, J =8.7, 2.8 Hz, 1H), 7.37 (d, J=8.7 Hz, 1H), 7.30 (dd, J=8.5, 2.1 Hz, 1H), 7.05 - 6.99 (m, 4H), 6.36 (ddd, J=17.3, 6.3, 1.5 Hz, 2H), 6.12 (ddd, J=17.5, 10.4, 7.3 Hz, 2H), 5.80 (ddd, J=10.4, 7.0 , 1.5 Hz, 2H), 4.15 (dt, J=8.6, 6.6 Hz, 4H), 4.07 (dt, J=12.6, 6.5 Hz, 4H), 1.89 - 1.79 (m, 4H), 1.71 (ddt, J= 14.1, 10.1, 6.8 Hz, 4H), 1.58 - 1.43 (m, 8H)

The exemplary compounds according to the present invention are summarized in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8

< Experimental Example 1 >

In order to evaluate the wavelength inverse dispersion of the compound synthesized through the example, the UV-visible absorbance was investigated. It is known that for the wavelength inverse dispersion of the compound, the major axis direction of the molecule should have the maximum absorption wavelength at a long wavelength, and the minor axis direction should have the maximum absorption wavelength at a shorter wavelength. At this time, the difference between the two absorption wavelengths should show a difference of 80 to 150 nm.

In order to determine the absorbance of the compound according to the present invention, the compound synthesized through the examples was dissolved in a solvent such as toluene and anisole, and the absorbance was measured at each wavelength from 200 nm to 700 nm, and the results are shown in Figure 1.

In Fig. 1, the Ne direction represents the absorption wavelength in the short-axis direction and serves as a reference. Specifically, it represents the absorption wavelength of the compound including the formyl group according to step 1 of Examples 1 to 4. Meanwhile, it can be seen that the compound according to the present invention has an absorption wavelength in the short-axis direction near 260 nm and an absorption wavelength in the long-axis direction near 360 to 380 nm.

Therefore, the compound according to the present invention has a difference of 100 to 120 nm in the maximum absorption wavelengths in the long and short axis directions of the molecule, which is sufficient to induce wavelength reverse dispersion, and thus can be usefully used as a material having reverse wavelength dispersion.

< Experimental example 2 >

To evaluate the alignment characteristics using the synthesized compound through the examples, a commercial alignment film (PIA-X189-KU1, JNC) was spin-coated on a washed glass substrate at 1300 rpm for 10 sec, 2000 rpm for 20 sec, and dried at 120 °C for 3 min and 230 °C for 1 h. After that, rubbing in one direction using an alignment cloth was performed, and a solution of a mixture of Example/LC242 dissolved in toluene at various ratios was spin-coated at 1300 rpm for 25 sec. The coated sample was dried at 100 °C for 3 min and irradiated with ultraviolet light (365 nm, 1.5 mW/cm ² ) for 20 min to form a film. The alignment state of the film can be evaluated by placing the film-formed sample between vertically intersecting polarizing plates and observing it with a polarizing optical microscope. As shown in FIG. 2, in the case of the example compound made through the present invention, it was confirmed that there was a difference in brightness when the polarizer was positioned between the polarizers with the alignment direction perpendicular to the polarizer on a polarizing optical microscope and when it was tilted at a 45 degree angle thereto, which means that the compound according to the example was well aligned on the alignment film.

The wavelength dispersion characteristics of the produced film were evaluated, and are shown in Fig. 3. The wavelength dispersion characteristics can be evaluated by calculating the phase retardation value of light incident on the film using a well-known method. The phase retardation value is defined as 2π Δn d / μ, where Δn is the birefringence, d is the thickness of the film, and μ is the wavelength. As shown in Fig. 3, it can be confirmed that when the host liquid crystal (LC242) and the example compound are mixed at a characteristic ratio or more, the phase retardation value increases (the birefringence increases) as the wavelength increases, exhibiting wavelength reverse dispersion characteristics.

Claims (12)

A reactive mesogen compound represented by the following chemical formula 1:
[Chemical Formula 1]

In the above chemical formula 1,
R is C _6-18 aryl or 5-14 atoms, unsubstituted or substituted with Y. Heteroaryl, where Y is C _6-18 aryl or 5-14 atoms substituted through vinylene. is heteroaryl;
A is one or more combinations selected from C=O, O, S, NH;
B is C _6-18 arylene;
C is L ² -C _1-20 alkylene, wherein L ² is one or more combinations selected from C=O, O, S, NH;
X is a photocrosslinkable functional group containing one or more radically polymerizable double bonds in the molecule.
In the first paragraph,
R is C _6-14 aryl, 5-14 atoms A compound which is a heteroaryl, or a C _6-14 aryl linked through vinylene.
In the first paragraph,
The above A is Person, compound.
In the first paragraph,
A compound wherein the above C is L ² -C _1-15 alkylene, and wherein L ² is O.
In the first paragraph,
The above X is Person, compound.
In the first paragraph,
wherein R is phenyl, naphthyl, anthracenyl, dibenzothiophenyl, or phenylethenylphenyl;
The two -ABCX are bonded so that they are para to each other in the benzene ring;
A is and;
B is phenylene;
C is OC _1-10 alkylene;
X is Person, compound.
In the first paragraph,
The above compound is a compound selected from the following:
;
;
;
;
;
;
;
.
As shown in the following reaction scheme 1,
A method comprising the step of producing a compound represented by chemical formula 1 by reacting a compound represented by chemical formula 2 with chemical formula 3.
Method for producing a compound represented by chemical formula 1:
[Reaction Formula 1]

In the above reaction formula 1,
R, A, B, C, and X are as defined in chemical formula 1 of the first paragraph.
A reverse wavelength dispersion polymerizable composition comprising the reactive mesogenic compound of claim 1.
A phase difference film manufactured from the composition of claim 9.
A liquid crystal film manufactured from the composition of claim 9.
An anti-reflection film manufactured from the phase difference film of Article 10.