KR101753754B1

KR101753754B1 - dipyrromethene-type compound, colorant compositions comprising the same, quencher for improving of contrast ratio comprising the same and color filter comprising the same

Info

Publication number: KR101753754B1
Application number: KR1020150108557A
Authority: KR
Inventors: 최재홍; 이현영; 권혜선; 오진규; 이혜민
Original assignee: 경북대학교 산학협력단
Priority date: 2015-07-31
Filing date: 2015-07-31
Publication date: 2017-07-05
Also published as: KR20170014731A

Abstract

TECHNICAL FIELD The present invention relates to a dipyramethylene-based compound, and more particularly, to a dipyramethylene-based compound represented by the following formula (1) or (2) and an isomer of the dipyramethylene metal complex .
[Chemical Formula 1]

(2)

Description

A dipyrromethene compound and a coloring composition comprising the same, a contrast enhancing quencher and a color filter comprising the same, colorant composition comprising the same,

TECHNICAL FIELD The present invention relates to a dipyramethylene-based compound, a coloring composition comprising the same, a colorless quencher for enhancing contrast ratio, and a color filter, and more particularly, to a dipyramethylene compound and a dipyrromethene-based compound which is an isomer of the dipyramethylene metal complex A coloring composition containing the same, a contrast ratio reducing retarder and a color filter.

A liquid crystal display device is an apparatus for displaying an image using the optical and electrical properties of a liquid crystal material. The light emitted from the light source is passed through a liquid crystal layer positioned between glass substrates to adjust transmittance, As it passes through a color filter, a full-color screen is realized by additive color mixing.

In the liquid crystal display device, a color filter uses three colors of red, green, and blue as a basis. For coloring, a yellow color is used for green and a violet color is used for blue.

Currently, color filters are mainly made of color resist based on a pigment dispersion milbase. The method of manufacturing a color filter by the pigment dispersion method is as follows. First, a color resist solution is coated on a substrate with a spin coater and dried to form a coating film. Then, colored pixels are formed by pattern exposure and development of the coating film. Thereafter, the colored pixel is subjected to a heat treatment at a high temperature to obtain a first color pattern, and this operation is repeated corresponding to the number of colors to produce a color filter.

In the case of the pigment dispersion method, since the color resist performance depends on the dispersion state of the pigment, stabilization of the pigment dispersion state requires not only a step of pigmenting the pigment powder but also an additive such as a dispersant and a pigment derivative, Thus, there is a limitation in using the pigment as a coloring agent to have a high luminance, a high contrast ratio, and a high resolution.

Accordingly, studies have been made to improve physical properties such as color characteristics, high transmittance, high brightness, and high contrast ratio by using a hybrid type colorant in which a dye is mixed with the pigment.

At this time, the dye should be easily dissolved in a common organic solvent and satisfactory heat resistance required in a culturing filter manufacturing process, as well as being mixed with other pigments and dyes, resulting in a high brightness and causing color change of the pigment and dye Should not. Furthermore, the dye should be able to solve the problem of reducing the contrast ratio due to the fluorescence emission of the auxiliary dye xanthene compound mixed in CI Pigment blue 15: 6 in the blue color region.

Accordingly, in order to solve the above-mentioned problems, the present invention is to provide a dipyrromethene compound.

Another object of the present invention is to provide a coloring composition characterized by containing the above-mentioned compound.

It is still another object of the present invention to provide a quenching agent for enhancing a contrast ratio, which comprises the above compound.

It is another object of the present invention to provide a color filter characterized by containing the above-mentioned compound.

According to an aspect of the present invention, there is provided a dipyrromethene compound, which is an isomer of a dipyramethylene metal complex compound represented by Chemical Formula 1 or 2 and an isomer of a dipyramethylene metal complex compound .

[Chemical Formula 1]

(2)

(Wherein R ₁ to R ₄ each independently represent a substituted or unsubstituted alkyl having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl having 1 to 30 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms A substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl ring having 5 to 30 carbon atoms; At least one of R ₁ to R ₄ is alkyl and M is selected from the group consisting of Zn, Cu, Mg, Fe, Si, Pt, Pd, Mo, Mn, Ni, Co, TiO, B and V = O And Y is a functional group capable of binding to the M, and is characterized by containing O.)

(Wherein R ₅ , R ₆ , R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl of 1 to 30 carbon atoms, A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl ring having 5 to 30 carbon atoms any selected one, and wherein R ₇ ~ R ₁₀ is substituted or unsubstituted, and substituted alkyl; M is Zn, Cu, Mg, Fe, Si, Pt, Pd, Mo, Mn, ni, Co, TiO, B and V = O). &Lt; / RTI >

In order to solve still another problem of the present invention, there is provided a coloring composition comprising the above compound, a quencher for enhancing the contrast ratio, and a color filter.

The dipyrromethene compound of the present invention is an isomer of the dipyramethylene metal complex compound and the dipyramethylene metal complex compound and is easily dissolved in an organic solvent such as propylene glycol methyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) Has heat resistance and has an advantage that it is mixed with other pigments and dyes to exhibit high brightness and does not cause color change of the pigments and dyes.

Accordingly, the dipyromethane-based compound may be included in the coloring composition, the contrast enhancing quencher, and the color filter.

In particular, the dipyramethine compound satisfies the solubility and heat resistance of an organic solvent required in an LCD color filter manufacturing process, and more particularly, The contrast ratio is prevented from being lowered and the contrast ratio is increased by 35 to 55%, thereby exhibiting a remarkable effect as a light-extinguishing agent for enhancing the contrast ratio.

1 is a graph showing the fluorescence inhibition rate of rhodamine B according to an embodiment of the present invention.

TECHNICAL FIELD The present invention relates to a dipyramethylene-based compound, a coloring composition containing the same, a colorless quencher for enhancing contrast ratio, and a color filter, and more particularly, to a dipyromethane-based compound and a dipyrromethene-based compound which is an isomer of the dipyramethylene metal complex A coloring composition containing the same, a contrast ratio reducing retarder and a color filter.

Hereinafter, the present invention will be described in detail.

The present invention relates to a dipyrammethene-based compound represented by the following formula (1) or (2) and an isomer of the dipyrammethene metal complex compound.

[Chemical Formula 1]

(2)

In Formula 1, R ₁ to R ₄ each independently represent a substituted or unsubstituted alkyl having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl having 1 to 30 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms Substituted or unsubstituted C6-C30 arylalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylalkyl, and substituted or unsubstituted C6-C30 heteroaliphatic ring, At least one of R ₁ to R ₄ is alkyl; M is any one metal or metal compound selected from the group consisting of Zn, Cu, Mg, Fe, Si, Pt, Pd, Mo, Mn, Ni, Co, TiO, B and V = O; Y is a functional group capable of binding to the M, and is characterized by containing O.

Wherein R ₅ , R ₆ , R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl of 1 to 30 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted C6-C20 aryl, a substituted or unsubstituted C6-C30 arylalkyl, and a substituted or unsubstituted C3-C20 aliphatic ring, a substituted or unsubstituted C6-C20 aryl, And R ₇ to R ₁₀ are substituted or unsubstituted alkyl; M is any one metal or metal compound selected from the group consisting of Zn, Cu, Mg, Fe, Si, Pt, Pd, Mo, Mn, Ni, Co, TiO, B and V =

The dipyramethylene-based compound of the present invention is an isomer of the dipyramethylene metal complex compound and the dipyramethylene metal complex compound represented by Chemical Formula 1 or Chemical Formula 2, and may be propylene glycol methyl ether acetate (PGMEA) and propylene glycol monomethyl ether PGME), and has heat resistance as the structure of the compound is maintained even at a high temperature of 200 ° C or higher.

Preferably, the dipyrromethene compound of the present invention exhibits a solubility of 3% by weight based on 100% by weight of the organic solvent, so that the dipyromethane compound can easily dissolve in an organic solvent for general color filters .

Also, preferably, the dipyramethylene compound of the present invention has a high decomposition temperature of 298 to 307 ° C, so that the compound is not deformed at a high temperature of 200 to 250 ° C, and mass change is minimized, .

In addition, the dipyrromethene compound of the present invention can be applied not only as a dye according to its own color but also as a coloring composition containing the dipyromethane compound. Specifically, the coloring composition containing the dipyramethylene-based compound is prepared by mixing the pigment with the dipyromethane-based compound dye to prepare a hybridized coloring composition, wherein the dipyromethane-based compound is easily mixed with the pigment, But does not cause color change of the pigment.

Since the present invention is a dipyramethylene-based compound represented by the above formula (1) or (2), it can be easily dissolved in an organic solvent, has excellent heat resistance and can be mixed with a pigment to form a coloring composition exhibiting high brightness, The color change of the coloring material does not occur.

Accordingly, a color filter containing the dipyramethylene-based compound can be produced.

Specifically, the color filter refers to a device for implementing a full-color screen by mixing light by passing light passing through a liquid crystal in a liquid crystal display device. The color filter is applied to the color filter The heat resistance is required, and in particular, it is necessary to prevent and reduce the reduction of the contrast ratio in order to display a clear full-color image by the additive color mixture.

Here, the contrast ratio means a ratio between a maximum value and a minimum value of brightness in an image of a television or the like, and is an important factor that affects the image quality of the display device. If the contrast ratio is increased, the contrast can be distinguished from a very bright color to a very dark color, so that the contrast can be expressed in detail and an excellent image quality can be realized.

Accordingly, the color filter containing the difromethene-based compound is easily applied to the heating process of the color filter as it has excellent heat resistance that the structure is not deformed at 200 DEG C or more. Also, since the compound itself can be applied as a dye, the dypyrromethene compound dye is mixed with a general color filter pigment to form a coloring composition and applied to a color filter, whereby the intrinsic color The characteristics can be maintained.

Further, since the above-mentioned dipyramethylene-based compound is included as a coloring agent of a blue filter in a color filter, a colorant of a conventional blue filter includes a xanthene-based compound, thereby overcoming the fact that the contrast ratio is reduced by fluorescence emission Of course, the contrast ratio can be increased and can be applied as a light-quenching agent for enhancing the contrast ratio.

In detail, the conventional blue filter includes a xanthene compound such as a small amount of CI pigment Violet 23 as a main component of CI pigment blue 15: 6, and thus, as a coloring agent, a fluorescence emitted by the xanthene- The contrast ratio is reduced. Accordingly, the present invention relates to a process for preparing a cyan pigment, which comprises adding the dipyrromethene compound of the present invention to a blue filter coloring agent containing CI pigment blue 15: 6 as a main component and containing a small amount of a xanthene compound pigment, The fluorescence is easily absorbed by the dipyromethane-based compound, thereby suppressing the fluorescence emission by 40 to 80%. Further, by suppressing the fluorescence emission, the contrast ratio can be prevented, and the contrast ratio can be increased by 35 to 55%.

More specifically, as the dipyromethane-based compound exhibits absorbance at a molar extinction coefficient of 55000 to 65000 at a wavelength of 550 to 600 nm at which the xanthene-based compound emits fluorescence, the fluorescence emitted by the xanthene- The phosphorescent compound is easily absorbed and the fluorescence emission is suppressed by 40 to 80%. As the fluorescence emission is suppressed, the contrast ratio can be prevented and the contrast ratio can be increased by 35 to 55%. Preferably, the absorption wavelength of the dipyramethylene compound is 550 to 650 nm.

The compound represented by the formula (1) is represented by the following formula.

The compound represented by the formula (2) is represented by the following formula.

Preferably, the compound represented by Formula 1 or Formula 2 is represented by the following formula.

More preferably, the compound represented by Formula 1 or Formula 2 is represented by the following formula.

Hereinafter, the present invention will be described in more detail with reference to Examples.

It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

<Examples>

Dipyrromethene-based compounds characterized in that they are isomers of dipyramethylene metal complexes and dipyramethylene metal complexes.

Example 1 Synthesis of intermediate

1-1. Synthesis of N- (3-cyano-4-phenyl-1H-pyrrol-2-yl)

Scheme 1 below shows a method for synthesizing N- (3-cyano-4-phenyl-1H-pyrrol-2-yl) acetamide.

(1) 2- (2-oxopropyl) isoindoline-1,3-dione

22.45 g (0.11 mol) of 2-bromo-1-phenylethanone was added to 30 ml of N, N-Dimethylacetamide and stirred at 40 ° C to prepare a compound solution. Next, 18.62 g (0.1) mol of phthalimide potassium was added to the compound solution while maintaining the temperature at 30 ° C, and the mixture was stirred at room temperature for 2 hours to complete the reaction, thereby preparing a reaction solution. After the reaction was completed, the reaction solution was poured into 300 ml of water to precipitate crystals. The precipitated crystals were filtered, washed with water, dried and recrystallized with methanol to obtain 2- (2-oxopropyl) isoindoline-1,3 -dione (1).

(2) 2-amino-4-methyl-1H-pyrrole-3-carbonitrile

4.31 g (0.021 mol) of the obtained 2- (2-oxopropyl) isoindoline-1,3-dione (1) and 1.82 (0.027 mol) of malononitrile were added to 22 L of ethanol and mixed with ice ). Next, 8.5 ml of 25% of the mass of the sodium methoxide methanol solution was added to the stirred solution, and the mixture was stirred for 1 hour to prepare a reaction solution. Further, the reaction solution was further stirred at room temperature for 1 hour so that the reaction could be terminated, and then refluxed for 4 hours.

Thereafter, the reaction solution was poured into 500 ml of water to precipitate crystals. The precipitated crystals were filtered, washed with water, dried and recrystallized from ethanol to obtain 2-amino-4-methyl-1H -pyrrole-3-carbonitrile (2).

(3) N- (3-cyano-4-phenyl-1H-pyrrol-2-yl) acetamide

2.62 g (0.014 mol) of the obtained 2-amino-4-methyl-1H-pyrrole-3-carbonitrile (2) was added to 13 ml of acetonitrile to prepare a dissolution solution. Then, 1.61 ml of acetic anhydride was added to the solution And the mixture was stirred at 50 ° C for 5 hours.

When stirring was completed, the crystals were precipitated by cooling at room temperature, and the precipitated crystals were washed with acetonitrile and dried to obtain N- (3-cyano-4-phenyl-1H-pyrrol- ).

[Reaction Scheme 1]

1-2. Synthesis of N- (3-cyano-4-phenyl-1H-pyrrol-2-yl) heptanamide

Hexaryl chloride was used instead of acetic anhydride in 2-amino-4-methyl-1H-pyrrole-3-carbonitrile (2) in the synthesis of N- (3-cyano-4-phenyl-1H- (3-cyano-4-phenyl-1H-pyrrol-2-yl) acetamide was obtained in the same manner as in the synthesis of N- (3-cyano- -pyrrol-2-yl) heptanamide (4) was synthesized and obtained.

The synthesis of N- (3-cyano-4-phenyl-1H-pyrrol-2-yl) heptanamide (4) is shown in Scheme 2 below.

[Reaction Scheme 2]

Synthesis of N- (3-cyano-4- (4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) heptanamide

Scheme 3 shows a method for synthesizing N- (3-cyano-4- (4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) heptanamide.

(1) 2-amino-1- (4- (diethylamino) phenyl) ethanone

0.01 mol of 2-bromo-1- (4- (diethylamino) phenyl) ethanone and 0.01 mol of hexamethylenetetramine were added to chloroform, refluxed for 4 hours, Upon completion of the reaction, an adduct was obtained by filtration.

Next, the resultant adduct was put into a HCl / methanol solution and refluxed for 1 hour. When the reaction was completed, the produced crystals were filtered to obtain 2-amino-1- (4- (diethylamino) phenyl) ethanone 5).

(2) N- (2- (4- (diethylamino) phenyl) -2-oxoethyl) acetamide

0.01 mol of 2-amino-1- (4- (diethylamino) phenyl) ethanone (5) was added to THF, 0.02 mol of acetic anhydride and 0.002 mol of pyridine were added and the mixture was reacted at room temperature for 1 hour. The compound was added to ice water and layer separation was carried out using ethyl acetate. Next, the organic layer thus obtained was evaporated to obtain N- (2- (4- (diethylamino) phenyl) -2-oxoethyl) acetamide (6).

(3) 2-amino-4- (4-diethylamino) phenyl) -1H-pyrrole-3-carbonitrile

After adding 0.01 mol of N- (2- (4- (diethylamino) phenyl) -2-oxoethyl) acetamide (6) and 0.012 mol of malononitrile into methanol, 0.03 mol of sodium ethoxide was added and refluxed for 6 hours. Next, the reaction solution was poured into water to precipitate crystals, and the precipitated crystals were filtered to obtain 2-amino-4- (4-diethylamino) phenyl) -1H-pyrrole-3-carbonitrile .

(4) N- (3-cyano-4- (4- (diethylamino) phenyl) -1H-pyrrol-2-yl) heptanamide

0.01 mol of 2-amino-4- (4-diethylamino) phenyl) -1H-pyrrole-3-carbonitrile (7) was added to acetonitrile and 0.012 mol of hexaryl chloride was slowly added to the reaction solution. . Upon completion of the reaction, the mixture was filtered to obtain N- (3-cyano-4- (4- (diethylamino) phenyl) -1H-pyrrol-2-yl) heptanamide (8).

(5) N- (3-cyano-4- (4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) heptanamide

14 ml of phosporyl chloride was added to 20 ml of cooled DMF, stirred at room temperature for 30 minutes to prepare a reaction product, and the reaction product was cooled.

Then, 0.01 mol of N- (3-cyano-4- (4- (diethylamino) phenyl) -1H-pyrrol-2-yl) heptanamide (8) was dissolved in 5 ml of DMF, The reaction was allowed to proceed at room temperature for 1 hour. After completion of the reaction, the reaction product formed by the reaction was poured into ice water, adjusted to pH 4 with NaOH, and then layered using ethyl acetate. The organic layer was separated to obtain N - (3-cyano-4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) heptanamide (9).

[Reaction Scheme 3]

Synthesis of N - (3-cyano-4- (4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-

In the method for the synthesis of N- (3-cyano-4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) heptanamide (9) 4- (diethylamino) phenyl) -5- (4-methylphenyl) -1H-pyrrole-3-carbonitrile (7), except that acetic anhydride was used instead of hexaryl chloride. (3-cyano-4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2 -yl) acetamide (11) was synthesized and obtained.

The synthesis of N- (3-cyano-4- (4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) acetamide (11) is shown in Scheme 4 below.

[Reaction Scheme 4]

Example 2 Synthesis of Dipyrromethene Metal Complex Compound

Dipyrromethene metal complexes synthesized for each of the above formulas are synthesized by synthesizing dipyramethylene metal complexes represented by the following formula (1) or (2) using the intermediate prepared above, and shown in Tables 1 and 2 below .

[Chemical Formula 1]

(2)

M R ₁ R ₂ Y R ₃ R ₄ Example 2-1 Zn

OH CH ₃ CH ₃ Example 2-2 Zn

OH C ₆ H ₁₃ C ₆ H ₁₃ Example 2-3 Zn

CH ₃ OH C ₆ H ₁₃ C ₆ H ₁₃ Examples 2-4 Zn CH ₃ CH ₃ OH C ₆ H ₁₃ C ₆ H ₁₃ Example 2-5 Zn

OH C ₆ H ₁₃ C ₆ H ₁₃ Examples 2-6 Cu

OH C ₆ H ₁₃ C ₆ H ₁₃ Examples 2-7 Cu

CH ₃ OH C ₆ H ₁₃ C ₆ H ₁₃ Examples 2-8 Cu CH ₃ CH ₃ OH C ₆ H ₁₃ C ₆ H ₁₃ Examples 2-9 Cu

OH C ₆ H ₁₃ C ₆ H ₁₃

M R ₅ R ₆ R ₇ R ₈ R ₉ R ₁₀ R ₁₁ R ₁₂ Examples 2-10 Zn

HCOCH ₃ HCOCH ₃ HCOCH ₃ HCOCH ₃

Examples 2-1 to 2-10 shown in Tables 1 and 2 show the dipyrammethene metal complexes represented by Chemical Formula 1 or Chemical Formula 2, wherein the synthesis of the dipyramethylene metal complex corresponding to Chemical Formula 1 The synthesis method of the diphenylmethane metal complex corresponding to the formula 2 will be described with reference to the synthesis method of Example 2-10. Further, the dipyrammethene metal complexes of Examples 2-1 to 2-10 prepared above were obtained at 65 to 85%.

(1) Synthesis of 3,4-benzyl-2,5-cyano-1,6-carbonitrile zinc hydroxide dipyrromethene (Example 2-1)

The following Reaction Scheme 5 shows the synthesis of Example 2-1, 3,4-benzyl-2,5-cyano-1,6-carbonitrile zinc hydroxide dipyrromethene (13), which is an embodiment corresponding to Chemical Formula 1 of the dipyrammethene metal complex &Lt; / RTI >

1.0 g (0.0042 mol) of the N- (3-cyano-4-phenyl-1H-pyrrol-2-yl) acetamide (3) was dissolved in 4.2 ml of acetic anhydride and 0.31 g (0.0021 mol) of triethyl orthophomate And the mixture was stirred at room temperature to prepare a reaction product.

Next, 6.3 ml of trifluoroacetic acid was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. After the completion of the reaction, the reaction product was firstly added to 20 ml of ethyl acetate and then added to 75 ml of a solution prepared by adding 11.2 g of sodium bicarbonate to water. The mixture was stirred at room temperature for 2 hours.

The precipitated crystals were filtered, washed with ethylacetate, dried and then recrystallized using methanol / acetonitrile to obtain 3,4-benzyl-2,5-cyano-1,6-carbonitrile zinc hydroxide dipyrromethene (13) 2-ylidene) methyl-4-methyl-1H-pyrrole-3-carbonitrile (12) as an intermediate of (Z) -2-amino-5- Were synthesized.

2-amino-5 - ((5-amino-4-cyano-3-2H-pyrrol-2-ylidene) methyl-4-methyl-1H- pyrrole-3-carbonitrile (12) (0.0021 mol) of zinc acetate (II) was added to the reaction solution which had been dissolved in 50 ml of methanol, and the mixture was stirred at room temperature for 8 hours to prepare a reaction product.

To the reaction product, 100 ml of water was added, and the mixture was stirred at room temperature for 2 hours. The precipitated crystals were filtered, washed first with acetonitrile, and then washed with ethyl acetate twice. The crystals were then purified by silica gel column chromatography using a mixture of methanol / methylene chloride (1:10) as the eluent to give 3,4-benzyl-2,5-cyano-1,6-carbonitrile zinc hydroxide dipyrromethene (13) Of dipyramethylene metal complex were synthesized.

[Reaction Scheme 5]

(2) Synthesis of 3,4,9,10-benzyl-2,5,8,11-cyano-1,6,7,12-carbonitrile zinc dipyrromethene (Example 2-10)

The following Reaction Scheme 6 illustrates the preparation of the dipyrammethene metal complex according to Example 2-10, 3,4,9,10-benzyl-2,5,8,11-cyano-1,6,7 , 12-carbonitrile zinc dipyrromethene (14).

(14) is a method for synthesizing a dipyrammeter metal complex of 3,4-benzyl-2,5-cyano-1,6-carbonitrile zinc hydroxide dipyrromethene (13) (5-amino-4-cyano -3-2H-pyrrol-2-ylidene) methyl-4-methyl-1H-pyrrole-3-carbonitrile to the Zn (CH ₃ COO) ₂ instead of _{Zn (CH 3 COO) (12} ) ₂ < RTI ID = 0.0 > 2H2. &Lt; / _RTI >

[Reaction Scheme 6]

(3) Synthesis of 3-benzyl-2,5-cyano-4-diethylamino-1,6-carbonitrile zinc hydroxide dipyrromethene (Example 2-5)

The following Reaction Schemes 7 and 8 show examples of the dipromethene metal complex compound of Formula 1, 3-benzyl-2,5-cyano-4-diethylamino-1,6-carbonitrile zinc hydroxide dipyrromethene (16).

In this case, 0.01 mol of the above N- (3-cyano-4- (diethylamino) phenyl) -5-formyl-1H-pyrrol-2-yl) heptanamide (9) was dissolved in 5 ml of acetic anhydride, And 0.01 mol of N- (3-cyano-4-phenyl-1H-pyrrol-2-yl) heptanamide (4) was dissolved in 3 ml of acetic acid and 4 ml of trifluoreacetic acid to prepare Reactant 2, 2 was slowly added to the reactant 1, and the reaction was allowed to proceed at room temperature for 5 hours.

After the reaction was completed, the resulting reaction product was poured into water, adjusted to pH 4 with NaOH, layered with ethyl acetate, and the obtained organic layer was washed with NaCl and water After that, an intermediate (15) of the dipyramethylene-based metal complex was prepared by distillation.

Next, 0.01 mol of intermediate (15) of the dipyramethylene-based metal complex was dissolved in THF, 0.01 mol of zinc acetate dihydroxide was added, and the mixture was reacted at room temperature for 7 hours. When the reaction is completed, water is poured out to precipitate crystals. The crystals are filtered and washed with acetonitrile to obtain diphenylmethane metal complex containing N, N-diethylaminobenzene functional group, 3-benzyl-2,5-cyano-4- diethylamino-1,6-carbonitrile zinc hydroxide dipyrromethene (16).

[Reaction Scheme 7]

<Test Example>

Absorbance measurement

For the dipyrammethene metal complexes of Examples 2-1 to 2-10, the absorbance and the molar extinction coefficient were measured using an HP-8452A spectrophotometer, and the results are shown in Tables 3 and 4 below .

M R ₁ R ₂ R ₃ R ₄ Y

Example 2-1 Zn

CH ₃ CH ₃ OH 557 59,000 Example 2-2 Zn

C ₆ H ₁₃ C ₆ H ₁₃ OH 580 61,000 Example 2-3 Zn

CH ₃ C ₆ H ₁₃ C ₆ H ₁₃ OH 574 59,000 Examples 2-4 Zn CH ₃ CH ₃ C ₆ H ₁₃ C ₆ H ₁₃ OH 566 59,000 Example 2-5 Zn

C ₆ H ₁₃ C ₆ H ₁₃ OH 590 60,000 Examples 2-6 Cu

C ₆ H ₁₃ C ₆ H ₁₃ OH 620 62,000 Examples 2-7 Cu

CH ₃ C ₆ H ₁₃ C ₆ H ₁₃ OH 615 58,000 Examples 2-8 Cu CH ₃ CH ₃ C ₆ H ₁₃ C ₆ H ₁₃ OH 605 57,000 Examples 2-9 Cu

C ₆ H ₁₃ C ₆ H ₁₃ OH 630 61,000

M R ₅ R ₆ R ₇ R ₈ R ₉ R ₁₀ R ₁₁ R ₁₂

Examples 2-10 Zn

HCOCH ₃ HCOCH ₃ HCOCH ₃ HCOCH ₃

559 64000

Referring to Tables 3 and 4, it can be seen that the dipyrammethene metal complexes of Examples 2-1 to 2-10 exhibit the maximum absorption wavelength at 550 to 630 nm, It was found that the fluorescence emission wavelength range of Rhodamine B was overlapped with the range of 550 ~ 600nm.

Accordingly, when the dipyrromethene metal complexes of Examples 2-1 to 2-10 are included in the blue filter together with rhodamine B, it is considered that fluorescence emitted by rhodamine B can be easily absorbed .

Furthermore, as can be seen from Tables 3 and 4, the dipyrammethene metal complexes of Examples 2-1 to 2-10 exhibit a high molar extinction coefficient of 57000 to 64000, It is considered that fluorescence emission of the rhodamine B can be suppressed by absorbing the fluorescence emitted by B.

Measurement of fluorescence inhibition rate for Rhodamine B

Through the above absorbance measurement tests, Examples 2-1 to 2-10 exhibited a high molar extinction coefficient and an absorption wavelength overlapping the fluorescence emission wavelength range of rhodamine B, It was judged that fluorescence could be easily absorbed and thus fluorescence emission of rhodamine B could be suppressed.

In order to examine the degree of inhibition of fluorescence emission of Rhodamine B according to the above example, the fluorescence emission intensity of Rhodamine B was measured by adding 25 wt% of dipyrammethene metal complex of the above example to Rhodamine B.

In this case, the dipyrromethene metal complexes of Examples 2-5 and 2-9 were used as the examples. In order to more easily analyze the degree of fluorescence inhibition by the addition of the examples, Rhodamine B fluorescence emission intensity was also measured.

FIG. 1 is a graph showing the fluorescence inhibition rate of rhodamine B according to the above-described examples.

The fluorescence emission intensity of rhodamine B was about 20000 when the dipyrromethene metal complex was not included, and the dipyrromethene metal complexes of Examples 2-5 and 2-9 in rhodamine B The intensity of fluorescence emission of rhodamine B was remarkably decreased and it was confirmed that the fluorescence emission intensity of about 4800 and about 11600 was exhibited.

That is, by adding the dipyrammethene metal complex of Example 2-9 to rhodamine B, the fluorescence emission of rhodamine B can be inhibited by 42%, and in particular Rhodamine B is doped with dipyramide of Example 2-5 The incorporation of the tung metal complex was able to inhibit the fluorescence emission of rhodamine B by 76%.

Contrast ratio, color difference and viscosity measurement

Through the above tests, it was confirmed that Examples 2-1 to 2-10 suppressed the fluorescence emission of rhodamine B (Rhodamine B).

In order to examine the effect of the colorant containing Rhodamine B as a color filter as a quencher in the dipyrammethene complex of the present invention, CI Pigment Blue 15: 6 and Rhodamine B ), And the contrast ratio, color difference, and viscosity were measured.

Examples 2 to 5, Examples 2 to 7, and Examples 2 to 8 were used for the above Examples. CI Pigment Blue 15: 6: Rhodamine B: : One of the above examples was made to be 86: 6: 8.

In order to easily analyze the contrast ratio, the color difference meter and the viscosity according to the above examples, CI Pigment Blue 15: 6 and Rhodamine B, which did not include the above example, were used as a control group.

The color difference and the contrast ratio were measured for the thin film after each of the coloring agents including the control group and the example was coated to form the thin film.

That is, 2 g of a coloring agent containing a control or an example was added to 9.5 g of a solvent PGMEA, 3.5 g of an acrylic binder, 3.5 g of dipentaerythritol penta / hexaacrylate and 0.5 g of a photoinitiator ingacure-369 A color resist was prepared and spin-coated at 300 rpm for 10 minutes to form a thin film, and then the color difference and the contrast ratio were measured for the thin film.

Table 5 shows viscosity, color difference, and contrast ratio measurement results for the control group and the Example 2-5, the Example 2-7, and the Example 2-8, respectively.

Viscosity (Tpr) Luminance (Y) Contrasty Control group 2.13 10.24 9143 Example 2-5 2.21 10.24 13714 Examples 2-7 2.21 10.23 12526 Examples 2-8 2.21 10.25 13257

Referring to Table 5, Examples 2-5, 2-7, and 2-8 were prepared by mixing CI Pigment Blue 15: 6, which did not include the above Examples, and a colorant (Rhodamine B) (Control group), the contrast ratio was increased by 37 ~ 50% while the viscosity was slightly increased and the luminance was not changed.

That is, when the dipyrammethene metal complex is incorporated in a coloring agent and used as a color filter, the coloring agent can maintain a predetermined viscosity and high brightness, thereby remarkably increasing the contrast ratio of the contrast ratio without affecting the color, So that it can be distinguished.

NMR analysis

In order to confirm the structures of Examples 2-5, 2-7, and 2-8, which are the dipyrammethene metal complex compounds showing the effect of increasing the contrast ratio, ¹ H NMR analysis was performed. The NMR analysis was performed using a Bruker Avance digital spectrometer system (BRUKER, USA) and DMSO-d6 was used at 400 MHz in the measurement.

NMR analysis of Example 2-5

Example 2-5 _{0.92 (m, 6H, CH 3} ), 1.12 (m, 6H, CH 2), 1.29 (m, 8H, CH 2), 1.31 (m, 2H, CH 2), 1.32 (m _{, 4H, CH 2), 1.55} (t, 2H, CH 2), 2.04 (s, 1H, OH), 2.31 (t, 2H, CH 2), 3.41 (t, 4H, CH 2), 6.71 (d, 2H, ArH), 6.81 (s, 1H, H), 7.20 (d, 2H, ArH), 7.33 (d, Calculated for C ₄₁ H ₄₈ ZnN ₇ O ₃ C: 65.62 H: 6.45 N: 13.07 O: 6.40, MS 754 (100) Calculated for C 71.92 (s, 1H, NH) Found C: 64.98 H: 6.56 N: Respectively.

NMR analysis of Example 2-7

Example 2-7 _{0.90 (m, 6H, CH 3} ), 1.30 (m, 8H, CH 2), 1.31 (m, 2H, CH 2), 1.32 (m, 4H, CH 2), 1.53 (t _{, 2H, CH 2), 2.02} (s, 1H, OH), 2.31 (t, 2H, CH 2), 6.81 (s, 1H, H), 7.37 (d, 1H, ArH), 7.50 (m, 2H, ArH), 7.52 (m, 2H , ArH), 10.78 (s, 1H, NH), Found C: 62.41 H: 6.12 N: 12.74 O: 8.01 Calculated for C 32 H 37 CuN 6 O 3 C: 61.73 H: 5.85 N: 13.93 O: 7.96, MS 617 (100).

NMR analysis of Example 2-8

Example 2-7 _{0.90 (m, 6H, CH 3} ), 1.30 (m, 10H, CH 2), 1.31 (m, 2H, CH 2), 1.32 (m, 4H, CH 2), 1.51 (t _{, 2H, CH 2), 2.02} (s, 1H, OH), 2.07 (m, 3H, CH 3), 2.21 (m, 3H, CH 3), 2.31 (t, 2H, CH 2), 6.81 (s, 1H, H), 10.78 (s, 1H, NH), Found C: 62.39 H: 6.12 N: 13.87 O: 8.12 Calculated for C ₂₇ H ₃₅ CuN ₆ O ₃ C: 62.27 H: 6.04 N: MS 617 (100).

Heat resistance measurement

In order to confirm the heat resistance of the dipyrammethene metal complexes of the examples, Examples 2-2 to 2-9 were subjected to heat treatment in a temperature range of 200 ° C to 310 ° C, while the mass change and the decomposition temperature of the above Example were measured Respectively.

The results are summarized in Table 6 below.

mass% Decomposition Temperature (℃)
200 ℃ 230 ℃ Example 2-2 99.1 97.5 300 Example 2-3 99.3 98.1 305 Examples 2-4 99.2 98.0 298 Example 2-5 99.3 98.4 307 Examples 2-6 99.5 98.1 305 Examples 2-7 99.6 98.2 303 Examples 2-8 99.3 97.8 302 Examples 2-9 99.4 98.1 304

Referring to Table 6, it can be seen that, in Examples 2-2 to 2-9, the mass is maintained at 97.5% or more, and the average decomposition temperature of the dipyrammethene metal complex in the above example is 303 ° C, it was confirmed that the dipyrammethene metal complexes of Examples 2-2 to 2-9 had excellent heat resistance.

In addition, in the case of Example 2-5, not only the highest decomposition temperature was shown at 307 ° C, but the mass was maintained at 98.4% even at 230 ° C.

Solubility measurement

To confirm the solubility of the dipyrammethene metal complex in the organic solvent for the color filter, the amount of propylene glycol methyl ether acetate (PGMEA), which is an organic solvent for the color filter, The solubility of the dipyramethylene metal complex was measured.

The solubility was measured by adding the dipyrromethene metal complex of Example 2-5 to the PGMEA solvent, ultrasonically treating the resultant with an ultrasonic cleaner ME6500E for 5 minutes, then allowing the ultrasonicated solution to stand at room temperature for 48 hours , The presence or absence of precipitation in the solution, and the like.

Thus, it can be confirmed that the solubility of the compound of Example 2-5 is 3 wt%, and considering that the dye or the coloring agent is not easily dissolved in an organic solvent such as PGMEA, it can be used as a colorant of a color filter It is judged that the solubility of the above-mentioned Example 2-5 is excellent.

From the above results, it can be seen that the dipyrammethene metal complex of the present invention can inhibit fluorescence emission of rhodamine B by up to 76%, and when used as a color filter, the colorant maintains a certain viscosity and high brightness, And the contrast ratio, which is the contrast ratio, is remarkably increased. In addition, it was confirmed that the dipyrammethene metal complex was easily dissolved in an organic solvent such as propylene glycol methyl ether acetate (PGMEA) and had excellent heat resistance.

Accordingly, the present invention can be incorporated into a coloring composition, a contrast enhancing quencher, and a color filter, and in particular, the dipyromethane-based compound has excellent solubility in an organic solvent and improved heat resistance, It is considered that the physical properties of the color filter can be remarkably improved by being included in the LCD color filter by increasing the contrast ratio by 35 to 55% by easily absorbing the fluorescence emitted by the xanthene compound used as the auxiliary colorant.

While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And various modifications and variations are possible within the scope of the appended claims.

Claims

A dipyrromethene compound represented by the following formula:

Is synthesized by the following Reaction Scheme (7).
[Reaction Scheme 7]

A coloring composition, characterized by containing a compound according to claims 1 or 2.

A quenching agent for enhancing a contrast ratio, which comprises a compound according to any one of claims 1 to 3.

A color filter comprising a compound according to any one of claims 1 to 3.

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