WO2015174662A1

WO2015174662A1 - Dye comprising pyrromethene-boron complex compound

Info

Publication number: WO2015174662A1
Application number: PCT/KR2015/004350
Authority: WO
Inventors: 장유미; 박정호; 전석운; 강주식; 이송
Original assignee: 에스케이케미칼주식회사
Priority date: 2014-05-16
Filing date: 2015-04-29
Publication date: 2015-11-19
Also published as: KR20150131807A

Abstract

The present invention relates to dye comprising a pyrromethene-boron complex compound. Dye comprising a pyrromethene-boron complex compound, according to the present invention, has no fluorescence, has excellent light resistance and can absorb light of a particular wavelength and thus can be utilized for dye for display.

Description

Specification

FIELD OF THE INVENTION The present invention relates to a dye comprising a novel pyrromethene boron complex compound. More specifically, the pyrromethene has no fluorescence, is excellent in light resistance, and can absorb light of a specific wavelength. A dye for displays comprising a boron complex. BACKGROUND ART Liquid crystal displays (LCDs), plasma display panels (PDPs), organic light-emitting diodes (OLEDs), and the like are currently being used in television sets, mobile phones, and personal computers. It is widely used as various home / industrial displays such as computers.

An LCD is a light receiving device that displays an image by controlling the amount of light coming from the outside. Therefore, a backlight unit (BLU) in the form of a back light source that can maintain uniform brightness across the screen is required.

BLU is a device that can express information by supplying lamp light to LCD which does not light itself. It is located on the back of LCD.

In order to use the backlight unit of the LCD as a light source, it is necessary to make a white light source by using a suitable light source. For example, there is a method of generating white light by combining red, green, and blue light sources, or by mixing two kinds of light sources such as blue and yellow low to form white light. Combining red, green, and blue light sources can produce more complete white light, while being relatively expensive. On the other hand, the combination of blue and yellow light sources can reduce the cost, but the quality of the white light is worse than the previous method. Recently, white light is formed by combining two kinds of light sources, blue and yellow, which are easier to manufacture and cheaper than a method using red, green, and blue three-way light, and implement color using a color filter. This is being utilized.

0LED refers to a device that emits light by using electroluminescence which emits light when current flows through an organic compound. 0LEDs are attracting attention as next-generation flat panel displays because they can be driven at low voltages, are thin, have a wide viewing angle and fast response speed. 、

In order to use 0LED as a light source of a display, a method of realizing white light is required as in LCD, and white light is generated by combining red, green and blue light sources, or white light is formed by combining yellow light emitting material with blue 0LED. How to implement color with color filters? However, the method of implementing color with a color filter after forming white light has a problem in that the color purity is increased by blocking unnecessary light due to poor quality.

The phenomenon that the quality of the white light is lowered is due to the presence of light having a wavelength of 400 to 520 nm, preferably 500 to 520 nm, which does not appear in the white light due to the mixing of the red, green, and blue ternary light. When the light in the region is present, the color purity of adjacent blue and green colors is lowered. Therefore, if only the unnecessary region is selectively removed by using a compound absorbing the wavelength of the light region, excellent white light can be made through the combination of two kinds of light sources. Examples of the compound having absorption characteristics in the light region of 400 to 520 nm, preferably 500 to 520 nm, include cyanine compounds, rhodamine compounds, coumarin compounds, and porphyrin compounds. However, since the cyanine compound, the rhodamine compound, and the coumarin compound have a wide absorption region, they absorb some of the light even at wavelengths outside the selection region, so that the luminance is greatly reduced. In addition, the porphyrin-based compound has a narrow light absorption region and high absorbance, but structurally As a large absorption occurs not only in the selected region but also in other regions, it is difficult to use the material for improving color purity filter.

On the other hand, the pyrromethene-based boron complex has a narrow full width half maximum (FWHM), so that there is no separate absorbing region other than the main absorbing region, and various molecular designs are possible, and 400 to 520 nm, preferably depending on the substituent. Can selectively absorb only the 500 to 520 nm light region, and can realize fluorescence and high light resistance. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a dye comprising a pyrromethene boron complex that is non-fluorescent and excellent in light resistance and capable of absorbing light of a particular wavelength.

It is another object of the present invention to provide a display filter comprising the dye. In order to achieve the above object, the present invention provides a dye comprising a pyrromethene boron complex represented by the following formula (1):

[Formula 1]

In the above formula,

R ¹ to R ⁶ are each independently hydrogen; d- ₈ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; D- ₆ alkyl substituted with halogen; Substituted by halogen, C ₆ - ₂₀ aryl; Or Ci-6 alkoxy substituted with halogen, where n is an integer from 0 to 6; A is C ₆ - ₂₀ aryl is.

The present invention also provides a display filter comprising the dye. According to the present invention, the dye containing the pyrromethene boron complex represented by the formula (1) of the present invention is not fluorescent, excellent light resistance, and can absorb light of a specific wavelength, it can be usefully used as a dye for display. DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described in more detail.

The dye of the present invention comprises a pyrromethene boron complex represented by the following formula (1):

[Formula 1]

In the above formula,

R ¹ to R ⁶ are each independently hydrogen; d- ₈ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; D- ₆ alkyl substituted with halogen; Substituted by halogen, C ₆ - ₂₀ aryl; Or d- ₆ alkoxy substituted with halogen, where n is an integer from 0 to 6;

A is C ₆ - ₂₀ aryl is. In one example of the dye according to the present invention,

R ¹ to R ⁴ are each independently hydrogen or C- ₆ alkyl; R ⁵ is hydrogen; ₍₈ alkyl; C ₆ - ₂₀ aryl, or halogen substituted C ₆ - ₂₀ aryl; R ⁶ is a d- ₆ alkyl, wherein n is an integer from 0 to 4;

A is C ₆ - ₂₀ aryl is. In another example of the dye according to the invention,

R ¹ to R ⁴ are each independently hydrogen or d- ₆ alkyl;

R ⁵ is hydrogen; d- ₈ alkyl; Phenyl; Or phenyl substituted with halogen;

R ⁶ is Ci ᅳ ₆ alkyl, wherein n is an integer of 0 or 1;

A is a phenyl ring or a naphthalene ring. In another example of the dye according to the present invention,

R ¹ to R ⁴ are each independently hydrogen or Ci-6 alkyl;

R ⁵ is hydrogen; Ci-8 alkyl; Phenyl; Or phenyl substituted with halogen;

R ⁶ is d- ₆ alkyl, where n is an integer of 0 or 1;

A is a naphthalene ring. As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine unless otherwise noted.

As used herein, the term 'alkyl' refers to a straight or branched hydrocarbon moiety unless stated otherwise.

As used herein, the term 'alkoxy' means — ORa group, where Ra is alkyl as defined above. Specific examples include, but are not limited to, methoxy ethoxy, n-propoxy, isopropoxy, n-sub-special, t-sub-special and the like.

The term 'aryl' as used herein refers to an aromatic group including phenyl, naphthyl and the like, unless otherwise noted. Preferred examples of the pyrromethene boron complex compound may be represented by the following formula la to formula lj: la]

Formula Id

5

[Formula li]

The dye containing the pyrromethene boron complex compound represented by Formula 1 has a maximum absorption wavelength at the boundary between blue and green, the maximum absorption wavelength may be a wavelength of 400 nm to 520 nm, preferably 500 nm to 520 nm have.

The dye containing the pyrromethene boron complex compound represented by the formula (1) is excellent in light resistance. For example, the dye of the present invention is diluted to a concentration of 1, 000 ppm with a toluene solution and exposed to Xe lamp (650 W / m ² and 50 ^° C.) for 24 hours, and then diluted to 10 ppm, followed by UV / When the pigment residual ratio at the maximum absorption wavelength was measured using a VIS spectrophotometer, the pigment residual ratio was 90% or more, preferably _95¾ or more. In addition, the dye of the present invention was diluted with toluene solution to a concentration of 1, 000 ppm to Xe Lamp (650 W / ra ² and 50 ^° C).

When the pigment residual ratio was measured at a maximum absorption wavelength using a UV / VIS spectrophotometer after exposing it to 64 ppm after exposure for 64 hours, the pigment residual ratio was 80% or more, preferably 90% or more. appear. The dye containing the pyrromethene boron complex compound can be used in the manufacture of a display filter, and thus the present invention also provides a display filter comprising the dye.

The display filter may, for example, prepare a photosensitive coloring composition comprising the dye, apply the photosensitive coloring composition onto a substrate, heat-dry the applied composition to form a film, and then dry the desired film. After selective exposure using a mask of a shape, after development, it may be manufactured through a method of heating and curing the developed film, but is not limited thereto. The dye containing the pyrromethene boron complex compound represented by the formula (1) may be used alone or in combination of two or more, and may be used in addition to other auxiliary colorants such as pigments or dyes.

The auxiliary colorant may be used without particular limitation as long as it is an organic pigment or dye having high transparency, color clarity and heat resistance, and the organic pigment or dye may be used alone or in combination of two or more.

When the organic pigment is used, if necessary, the dye containing the compound of Formula 1 may be used by miniaturizing the particles by a method such as solvent salt milling, dry milling, acid paste, or the like as necessary.

In addition, when the organic pigment is used, a dispersant commonly used in the manufacture of a display filter for the dispersion of the organic pigment may be used together.

The dispersant may include, for example, an amine group or an ammonium salt group as a pigment affinity group. Preferably, an acrylic copolymer, polyurethane, polyethyleneimine, or a combination thereof may be used. Compound of formula 1 of the present invention can be prepared as shown below.

[Banungsik 1]

In the above formulas,

R ¹ to R ⁶ , A and n are the same as mentioned in the general formula (1). The preparation method of the compound of Formula 1 will be described in detail step by step. Step (1): Preparation of Intermediate Dichloromethane as a total of 2 equivalents of Compound (1) and / or Compound (1 '), 1 equivalent of Compound (2) and a solvent in a 1 L equilibrium bottom flask under nitrogen atmosphere was added at 12 to 36 at room temperature. Stir for time. 5 equivalents of triethylamine (TEA) and 6 equivalents of borontrifluoride diethyl ether (BF ₃ 0Et ₂ ) were added thereto, followed by stirring at room temperature for 2 to 6 hours. After the reaction was completed, water was added to separate the layers, the organic layer was concentrated, and then subjected to column chromatography using a mixed solvent of dichloromethane and nucleic acid, thereby obtaining Compound (3) as an intermediate. Step (2): Preparation of Pyrromethene Boron Complex Compound 2 equivalents of aluminum chloride (A1C1 ₃ ) and dichloromethane (DCM) as a solvent are added to 1 equivalent of compound (3), which is the intermediate obtained in step (1), and 1 to After stirring for 20 minutes, 5 equivalents of Compound (4) was added, followed by stirring at room temperature for 10 minutes to 1 hour. After the reaction was completed, water was added to separate the layers, the organic layer was concentrated, and column chromatography was performed using a mixture of dichloromethane and nucleic acid to obtain the compound of Formula 1. EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention and the scope of the present invention is not limited thereto. Example 1: Preparation of Compound of Formula la (1): Preparation of Intermediate (1)

15.0 g of 2,4-dimethylpi in a 1 L equidistant bottom flask under a nitrogen atmosphere

(158 mmol), 6.2 g (79 mmol) of acetyl chloride, and 450 ml of dichloromethane were added thereto, followed by stirring at room temperature for 24 hours. 55 ml of triethylamine and 55 ml of boron trifluoride diethyl ether were added thereto, followed by stirring at room temperature for 4 hours. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 9.4 g of an intermediate solid (1). ) (Yield 45%). The maximum absorption wavelength in methyl ethyl ketone (MEK) of the intermediate (1) was 494 nm. ： Preparation of compound (la)

1.3 g (10 mmol) of aluminum chloride and 100 ml of dichloromethane were added to 1.3 g (5 mmol) of the intermediate (1) obtained in step (1), followed by stirring at room temperature for 5 minutes, followed by 1, 2-dihydroxybenzene 2.8 g (25 mmol) was added thereto, followed by stirring at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to obtain 1.4 g of the compound of formula la as an orange solid. Obtained (yield: 83%). Maximum absorption wavelength was 500 nm in MEK.

1.3 g (10 mmol) of aluminum chloride and 100 ml of dichloromethane were added to 1.3 g (5 mmol) of the intermediate (1) obtained in the step (1) of Example 1, followed by stirring at room temperature for 5 minutes, followed by butylcatechol 4.2. g (25 mmol) was added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give an orange solid, 1.7 g of a compound of the formula lb. Was obtained (yield: 87%). Maximum absorption wavelength was 500 nm in MEK.

1.3 g (10 mmol) of aluminum chloride and 100 ml of dichloromethane were added to 1.3 g (5 mmol) of the intermediate (1) obtained in the step (1) of Example 1, followed by stirring at room temperature for 5 minutes, 2,3 -4.0 g (25 mmol) of dihydroxynaphthalene was added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give an orange solid, 1.5 g of the compound of formula lc. Was obtained (yield: 77%). Maximum absorption wavelength was 500 nm in MEK. Example 4: Preparation of Compound of Formula (Id) Step (1): Preparation of Intermediate (2)

(158 mmol), / r-octylchloride 14.0 g (79 mmol), and 450 ml of dichloromethane were added thereto, and the resultant was stirred at room temperature for 24 hours. 55 ml of triethylamine and 55 ml of boron trifluoride diethyl ether were added thereto, followed by stirring at room temperature for 4 hours. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)). This was carried out to obtain 9.4 g of Intermediate (2) as a red solid (yield 45%).

The maximum absorption wavelength of intermediate (2) was 495 nra in MEK. Step (2): Preparation of Compound Molar (Id)

To 1.8 g (5 mmol) of the intermediate (2) obtained in step (1), add 1.3 g (10 mmol) of aluminum chlorad and 100 ml of dichloromethane, and stir at room temperature for 5 minutes, followed by 1,2-dihydroxy 2.8 g (25 mmol) of benzene was added and stirred at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 1.5 g of the compound of formula Id as an orange solid. Obtained (yield: 72¾. Maximum absorption wavelength was 501 nm in MEK. Example 5 Preparation of Compound of Formula le (1): Preparation of Compound (3)

16.8 g of 2,4-dimethylpi in a 1 L back-bottom flask under a nitrogen atmosphere

(177 mmol), 12.4 g (88 mmol) of benzoyl chloride and 500 ml of dichloromethane were added thereto, and the resultant was stirred at room temperature for 24 hours. 62 ml of triethylamine, Boron trifluoride diethyl ether 62 ral was added thereto, followed by stirring at room temperature for 4 hours. Subsequently, water was added to separate the layers, and then the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give an orange solid, 11.2 g of intermediate (3). Was obtained (yield 39%). Maximum absorption wavelength was 499 nm in MEK.

1.6 g (5 觀 ol) of intermediate (3) obtained in step (1), 1.3 g (10 mraol) of aluminum chloride, and 100 ml of dichloromethane were added and stirred at room temperature for 5 minutes, followed by 1,2-dihydroxybenzene 2.8 g (25 mmol) was added thereto, followed by stirring for 30 minutes at silver. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 1.5 g of the compound of formula le as an orange solid. Obtained (yield: 74%). Maximum absorption wavelength was 505 nm in MEK. Preparation of Compounds of Formula H

1.6 g (5 ramol) of the intermediate (3) obtained in the step (1) of Example 4, 1.3 g (10 μl ol) of aluminum chloride and 100 ni of dichloromethane were added thereto, and stirred at room temperature for 5 minutes. Then, 4.2 g (25 μl) of butylcatechol was added thereto and stirred at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 1.8 g of the compound of formula H as an orange solid. Obtained (yield: 80%). Maximum absorption wavelength was 504 nm in MEK. 7: Preparation of the compound of formula lg

1.6 g (5 mmol) of the intermediate (3) obtained in the step (1) of Example 4, 1.3 g (10 mmol) of aluminum chloride, and 100 ml of dichloromethane were added thereto, and stirred at room temperature for 5 minutes, followed by 2, 3-di 4.0 g (25 Pa ol) of hydroxynaphthalene was added thereto, followed by stirring at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 1.8 g of the compound of formula lg as an orange solid. Obtained (yield: 82%). Maximum absorption wavelength was 505 nm in MEK. Example 8 Preparation of Compound of Formula (lh) Step (1): Preparation of Intermediate (4)

7.1 g (75 mmol) of 2, 4-dimethylpi, 10.1 g (38 kol) of 4-iodobenzoyl chloride, and 250 ml of dichloromethane were added to a 500 ml back bottom flask in a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 hours. 26 ml of triethylamine and 26 ΓΠΓ of boron trifluoride diethyl ether were added thereto, followed by stirring at room temperature for 4 hours. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 5.0 g of an orange solid intermediate (4). Obtained (yield 29%). The maximum hop wavelength was 501 nm in MEK. ： Preparation of compound (lh)

2.3 g (5 mmol) of the intermediate (4) obtained in the step (1), 1.3 g (10 mmol) of aluminum chloride, and 100 ml of dichloromethane were added thereto, and stirred at room temperature for 5 minutes, followed by 1, 2-dihydroxybenzene 2.8 g (25 mmol) was added thereto and stirred at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 2.1 g of the compound of formula lh as an orange solid. (Number: 79%). Maximum absorption wavelength was 506 nm in MEK. Example 9 Preparation of a Compound of Formula Li (1): Preparation of Intermediate (5)

6.1 g (75 tnmol) of 2-methylpi, 5.3 g (38 kPa) of benzoyl chloride, and 250 ml of dichloromethane were added to a 1 L equilateral bottom polar flask under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 hours. 26 ml of triethylamine and 26 ml of boron trifluoride diethyl ether were added thereto, followed by stirring at room temperature for 4 hours. After the reaction was completed, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give an orange solid (5) 4.5 g. Was obtained (yield: 40%). Maximum absorption wavelength was 509 nm in MEK.

1.5 g (5 μl ol) of intermediate (5) in step (1), aluminum chloride

1.3 g (10 mmol) and 100 ml of dichloromethane were added and stirred at room temperature for 5 minutes.

2,8 g (25 mmol) of 1,2-dihydroxybenzene was added thereto, followed by stirring at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give an orange solid, 1.5 g of the compound of formula li. Was obtained (yield: 84%). Maximum absorption wavelength was 515 nm in MEK. Example 10 Preparation of a Compound of Formula lj Step α): Preparation of Intermediate (6)

In a nitrogen atmosphere, a 1 L back bottom flask was charged with 6.1 g (75 mmol) of 2 g methyl pi, 6.0 g (38 mmol) of 4-polourobenzoyl chloride and 250 ml of dichloromethane, and stirred at room temperature for 24 hours. 26 ml of triethylamine and 26 ml of boron trifluoride diethyl ether were added thereto, followed by stirring for 4 hours at phase silver. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 3.8 g of an intermediate (6) as an orange solid. Obtained (yield: 32%). Maximum absorption wavelength was 510 nm in MEK. Step (2): Preparation of Compound (li)

In step (1), 1.6 g (5 mmol) of intermediate (6), 1.3 g (10 g) of aluminum chloride, and 100 ml of dichloromethane were added thereto, and the resultant was stirred for 5 minutes at silver, followed by 1,2-dihydroxybenzene 2.8 g (25 mmol) was added thereto, followed by stirring at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give 1.5 g of the compound of formula lj as an orange solid. Obtained (yield: 78%). Maximum absorption wavelength was 516 nm in MEK. Comparative Example 1 Preparation of Comparative Compound 1 Preparation of Intermediate

2,4-dimethyl-3-ethylpi was placed in a 1 L back bottom flask under a nitrogen atmosphere.

9.2 g (75 g οΐλ acetyl chloride 3.0 g (38 g ol) and 250 ml of dichloromethane were added and stirred at room temperature for 24 hours, followed by 26 ml of triethylamine and 26 ml of boron trifluoride diethyl ether. After stirring for 4 hours at room temperature, water was added to separate the layers, the organic layer was concentrated, and then column chromatography was performed with a mixture of dichloromethane and nucleic acid to give 3.9 g of an intermediate solid (1 '). (Yield: 32. The maximum absorption wavelength was 517 nm in MEK. Step (2): Preparation of Comparative Compound 1

1.6 g (5 mmol) of the intermediate (1 ') obtained in step (1), 1.3 g (10 mmol) of aluminum chloride, and 100 ml of dichloromethane were added thereto, and the mixture was stirred at room temperature for 5 minutes, followed by 1, 2-dihydroxybenzene 2.8 g (25 mmol) was added thereto, followed by stirring at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) was performed to obtain 1.5 g of Comparative Compound 1 as an orange solid (yield: 75 %). Maximum absorption wavelength was 523 nm in MEK. Comparative Example 2: Preparation of Comparative Compound 2 Preparation of ')

In a 1 L back bottom flask under nitrogen atmosphere, add 9.2 g (75 mmol) of 2,4-dimethyl-3-ethylpyri, 6.7 g (38 隱 ol) of 4—chlorobenzoyl chloride, and 250 ml of dichloromethane. Stirred for time. 26 ml of triethylamine and 26 ml of boron trifluoride diethyl ether were added thereto, followed by stirring at room temperature for 4 hours. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to give a red solid intermediate (2 ') 6.5. g was obtained (yield: 41%). Maximum absorption wavelength was 523 nm in MEK. Step (2): Preparation of Comparative Compound 2

2.1 g (5 mmol) of the intermediate (2 ') obtained in step (1), 1.3 _g (10 μl ol) of aluminum chloride, and 100 ml of dichloromethane were added thereto, and stirred at room temperature for 5 minutes, followed by 1,2-dihydroxybenzene 2.8 g (25 mmol) was added thereto and stirred at room temperature for 30 minutes. Subsequently, water was added to separate the layers, and the organic layer was concentrated. Then, column chromatography was performed with a mixed solvent of dichloromethane and nucleic acid (1: 2 (v / v)) to obtain 1.7 g of Comparative Compound 2 as an orange solid. (Yield: 72%). Maximum absorption wavelength was 529 nm in MEK. Test Example 1 Test Example 1 Maximum Absorption Wavelength, Absorption Coefficient, and Half Width Measurements The compounds of Examples 1 to 10, the intermediate (1) prepared in Step (1) of Example 1, and the Preparation of Step (1) of Example 5 One intermediate (3) and the compounds of Comparative Examples 1 and 2 were diluted with methyl ethyl ketone (MEK) at a concentration of 10 ppm and the maximum absorption wavelength was measured with a UV / VIS spectrophotometer (Perkinelmer, Lamda25).

Gram extinction coefficient (ml / gcm) was calculated according to Beer's law for absorbance units obtained by measuring a 10 ppm solution with a cuvette of 10 mm optical path length. In addition, the half width (nm), which is an area where absorption at each maximum absorption wavelength is halved, was measured. Test Example 2: Calculation of Fluorescence Quantum Yield (PL) The compound of Examples 1 to 10, the intermediate prepared in step (1) of Example 1, the intermediate prepared in step (1) of Example 5 ( 3), and the compounds of Comparative Examples 1 and 2 were diluted with methanol to measure PUPerkinelmer, LS-55) and the fluorescence quantum yield (Φ) was calculated. In Table 1 below, the compound of Examples 1 to 10, the intermediate (1) prepared in step (1) of Example 1, the intermediate (3) prepared in step (1) of Example 5, and Comparative Example 1 Together with the structure of the compound of Example 2, the maximum absorption wavelength, extinction coefficient, half width and fluorescence quantum yield in MEK are shown.

Table 11

n-Octyl.

Example 4 501 1.8X10 ⁵ 23 nd

Example 5 505 2.1X10 ⁵ 20 nd

Example 6 504 2.0X10 ⁵ 21 nd

Example 7 Γ Λ 505 2.0X10 ⁵ 20 nd

Example 8 506 1.8X10 ⁵ 22 nd

Example 9 515 2.2X10 ⁵ 21 nd

Test Example 3: Evaluation of Light Resistance The compounds of Examples 1 to 4, the intermediate (1) prepared in step (1) of Example 1, and the intermediate (3) prepared in step (1) of Example 5 were each made of toluene. After diluting the solution to a concentration of 1,000 ppm, it was exposed to Xe lamps (650 W / m ² , 50 ^° C.) for 24 hours and 64 hours, respectively.

After diluting this at a concentration of lOppm, the pigment residual ratio at the maximum absorption wavelength was measured using a UV / VIS spectrophotometer (Perkinelmer, Lamda25). The results are shown in Table 2.

Table 2

As can be seen from Table 1, the pyrromethene boron complex according to the present invention has a maximum absorption wavelength in the range of 480 to 520 nm, and a narrow half-value width, so that the color purity of the blue and green color of the display to which the display filter is applied is included. It can optionally be improved.

In addition, it can be seen from Table 1 that the pyrromethene boron complex according to the present invention has no fluorescence, and from Table 2 it can be seen that the pyrromethene boron complex according to the present invention has excellent light resistance.

Claims

Scope of claim

1. A dye comprising a pyrromethene boron complex compound represented by Formula 1 below:

[Formula 1]

In the above formula,

R ¹ to R ⁶ are each independently hydrogen; d- ₈ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; D- ₆ alkyl substituted with halogen; Substituted by halogen, C ₆ - ₂₀ aryl; Or d- ₆ alkoxy substituted with halogen, where n is an integer from 0 to 6; A is C ₆ - ₂₀ aryl is. The method of claim 1,

R ¹ to R ⁴ are each independently hydrogen or d- ₆ alkyl;

R ⁵ is hydrogen; d- ₈ alkyl; C ₆ - ₂₀ aryl; Or substituted by halogen, C ₆ - ₂₀ aryl;

R ⁶ is d-6 alkyl, wherein n is an integer from 0 to 4;

A is C ₆ - ₂₀ aryl dyes. The method of claim 1,

R ¹ to R ⁴ are each independently hydrogen or d- ₆ alkyl;

R ⁵ is hydrogen; d- ₈ alkyl; Phenyl; Or phenyl substituted with halogen;

R ⁶ is Ci-6 alkyl, wherein n is an integer of 0 or 1;

A is a phenyl ring or a naphthalene ring. The method of claim 1 R ¹ to R ⁴ are each independently hydrogen or d- ₆ alkyl;

R ⁵ is hydrogen; d- ₈ alkyl; Phenyl; Or phenyl substituted with halogen;

R ⁶ is d- ₆ alkyl, where n is an integer of 0 or 1;

A dye is a naphthalene ring. Tax in Clause 1

The dye of the pyrromethene boron complex is any one of compounds selected from the group of the following formula la to lj:

Formula Id

[Formula le]

[Formula lh]

6. In accordance with paragraph 1,

The dye having a maximum absorption wavelength of 400-520 nm.

7. Paragraph 1 according to claim 1,

The dye was distilled off to a concentration of 1,000 ppm in a toluene solution. After 24 hours of exposure to Xe lamps (650 ff / m ² and 50 ^° C), and again diluting it to 10 ppm, the pigment residual ratio at the maximum absorption wavelength was measured using a UV / VIS spectrophotometer. Dye with a pigment residual of 90% or more.

8. The method of paragraph 1,

The dye was distilled off to a concentration of 1,000 ppm in a toluene solution.

When exposed to Xe lamp (650 W / m ² and 50 ^° C) for 64 hours, and then again distilled to 10 ppm, the pigment residual ratio at the maximum absorption wavelength was measured using a UV / VIS spectrophotometer, Dye with a pigment residual of 80% or more.

9. A display filter comprising the dye according to any one of claims 1 to 8.