KR20140013967A - Dyes for a color filter - Google Patents

Abstract

The present invention provides a dye for a color filter comprising the acidic dye (A) represented by the formula (1) and the basic dye (B) represented by the formula (2) and a method for producing the same.

Description

Dye for color filter {DYES FOR A COLOR FILTER}

The present invention relates to a color filter dye which is free of foreign matters and has little color change at a high temperature even when included in a colored photosensitive resin composition alone or together with a pigment as a dye.

A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. In particular, in recent years, the use of LCD has been further expanded. Accordingly, color filters have been recognized as one of the most important parts in reproducing color tone of LCDs.

Such a color filter is manufactured by the method of forming a desired coloring pattern using the coloring photosensitive resin composition containing a coloring agent. Specifically, it is produced by forming a coating layer made of a colored photosensitive resin composition on a substrate, repeating a series of processes of forming a pattern on the formed coating layer, exposing and developing, heating and thermosetting.

As a colorant, pigments have been used, but in recent years, attempts have been made to use dyes having high brightness and excellent heat resistance. The use of only a dye as a coloring agent is preferable because it can realize all the excellent characteristics of a dye, but the use of the dye is limited because the compatibility with other components of the composition is worse than that of the pigment and the color change is large at high temperatures. Therefore, a method of using a hybrid type colorant using both a pigment and a dye as a colorant has been attempted, but until now, the problem of using a colorant including a dye has not been completely solved.

In the case of manufacturing a color filter using a coloring photosensitive resin composition containing a dye as a coloring agent, decolorization or color change occurs during a post-process at a high temperature, and foreign substances are formed when forming a colored layer due to lack of compatibility with materials used. Occurs. In addition, when a color filter is manufactured, the developing speed is low and the sensitivity is insufficient, so that the pattern formed during the development process by the alkaline developer often peels off. Therefore, there is a need for development of a colored photosensitive resin composition suitable for a lyso process that can solve the problem of including a dye as a colorant or using a dye alone as a colorant.

As a coloring photosensitive resin composition using the conventional dye, there exists a blue coloring composition for color filters of Korea Patent Publication No. 10-2011-0061490. The blue coloring composition for color filters contains a binder resin and a coloring agent, and the coloring agent includes a blue pigment and a salt forming product, and the salt forming product is formed from a compound having a xanthene-based acid dye and a cationic group. In the case of the salt forming product, there is a problem that can not ensure satisfactory heat resistance when forming the color filter.

In addition, as an attempt to secure the heat resistance of the dye, there has been an attempt to make the dye insoluble pigment, as in Japanese Patent Application Laid-Open No. 2012-87293.

Republic of Korea Patent Publication No. 10-2011-0061490 Japanese Patent 2012-87293A

The present invention is to solve the problems of the prior art as described above, even when used alone or in combination with a pigment, color filter dyes for color filters having no foreign matters and excellent heat resistance at the time of manufacturing the color filler and less color change at high temperature The purpose is to provide.

The present invention

It provides a dye for a color filter comprising an ionic compound of the acid dye (A) represented by the formula (1) and the basic dye (B) represented by the formula (2):

(Formula 1)

Where

m and n are integers of 1 to 3,

X ⁺ is a monovalent to trivalent cation,

R ₁ to R ₆ are each independently hydrogen, hydroxy, amine, -SO ₃ ^- and, -SO ₃ H, a substituted or unsubstituted alkyl of C1 ~ C6 ring, or -NR ^a R ^b, where R ^a and R ^b is each independently Hydrogen, substituted or unsubstituted C1-C6 alkyl, C3-C12 cycloalkyl, C5-C30 aryl, or C5-C30 heteroaryl, wherein C3-C12 cycloalkyl, C5-C30 aryl, and a C5 ~ C30 aliphatic or aromatic ring of the heteroaryl group is a substituted or unsubstituted C1 ~ C20 ^{_{alkyl, -SO 3 -, -SO 3 H}} , -CO 2 -, -SO 2 R c And -NR ^d R ^e is unsubstituted or substituted with one or more selected from the group consisting of R ^c , R ^d and R ^e are each independently hydrogen, substituted or unsubstituted C 1 -C 6 alkyl, —CH ₂ ═CH ₂ , —C (═O) R ^f , — (CH 2) o O—SO ₃ ^— , or tria Is a radical group, wherein R ^f is a substituted or unsubstituted C1-C6 alkyl group, the triazine group is unsubstituted or substituted with one or more substituents selected from a phenylamine group substituted with a halogen element and a sulfonate anion, and o is An integer of 1 to 5;

(Formula 2)

In the above formula

m and n are integers of 1 to 3,

Y ⁻ is a monovalent to trivalent anion,

R ₀ is benzene or naphthalene,

R _p is thiophene or benzothiophene,

R _{1 ,} R _{2 ,} R _{3 ,} R _{4 ,} R _{5 ,} and R ₆ is hydrogen, each independently a substituted or unsubstituted C 1 -C 6 linear or cyclic alkyl group, or a phenyl group.

In addition,

(a) dissolving an acidic dye (A) represented by Formula 1 in deionized water to prepare an acidic dye (A) solution;

(b) dissolving the basic dye (B) of Chemical Formula 2 in deionized water to prepare a basic dye (B) solution;

(c) dropping a basic dye (B) solution into the acid dye (A) solution;

(d) performing filtration after completion of the reaction of step (c) and washing the filtrate with deionized water; And

(e) it provides a method for producing a dye for color filters comprising the step of drying the washed filtrate.

The color filter dye according to the present invention is used alone or included with the pigment as a colorant, there is no foreign matter in the manufacture of the color filler and excellent heat resistance exhibits a characteristic of less color change at high temperatures.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a dye for a color filter comprising an ion-bonding compound of an acid dye represented by the following formula (A) and a basic dye represented by the following formula (B):

(Formula 1)

Where

m and n are integers of 1 to 3,

X ⁺ is a monovalent to trivalent cation,

R ₁ to R ₆ are each independently hydrogen, hydroxy, amine, -SO ₃ ^- and, -SO ₃ H, a substituted or unsubstituted alkyl of C1 ~ C6 ring, or -NR ^a R ^b, where R ^a and R ^b is each independently Hydrogen, substituted or unsubstituted C1-C6 alkyl, C3-C12 cycloalkyl, C5-C30 aryl, or C5-C30 heteroaryl, wherein C3-C12 cycloalkyl, C5-C30 aryl, and a C5 ~ C30 aliphatic or aromatic ring of the heteroaryl group is a substituted or unsubstituted C1 ~ C20 ^{_{alkyl, -SO 3 -, -SO 3 H}} , -CO 2 -, -SO 2 R c And -NR ^d R ^e is unsubstituted or substituted with one or more selected from the group consisting of R ^c , R ^d and R ^e are each independently hydrogen, substituted or unsubstituted C 1 -C 6 alkyl, —CH ₂ ═CH ₂ , —C (═O) R ^f , — (CH 2) o O—SO ₃ ^— , or tria Is a radical group, wherein R ^f is a substituted or unsubstituted C1-C6 alkyl group, the triazine group is unsubstituted or substituted with one or more substituents selected from a phenylamine group substituted with a halogen element and a sulfonate anion, and o is It is an integer of 1-5.

In the roneun X ⁺ e. G., Na ^+, may be made of K ^+, NH ₄ ^+, Ca ^{2 +,} or the like, the aryl group is a phenyl group or a naphthalene group can be preferably used.

(Formula 2)

In the above formula

m and n are integers of 1 to 3,

Y ⁻ is a monovalent to trivalent anion,

R ₀ is benzene or naphthalene,

R _p is Thiophene (C ₄ H ₄ S) or Benzothiophene (C ₈ H ₆ S),

R _{1 ,} R _{2 ,} R _{3 ,} R _{4 ,} R _{5 ,} and R ₆ is hydrogen, each independently a substituted or unsubstituted C 1 -C 6 linear or cyclic alkyl group, or a phenyl group.

Roneun for example, Cl ^{- -} in the ^{Y, I -, Br -, HSO} 4 -, OH - and the like, the aryl group is a phenyl group or a naphthalene group can be preferably used.

Hereinafter, specific acid dyes (A) and basic dyes (B) will be described.

Acid dyes (A)

The acid dye (A) is not particularly limited as long as it is an anthraquinone acid dye including a sulfonate or carboxylate, and a preferred example of the anthraquinone acid dye in the acid dye (A) is CI acid blue 25, CI acid blue 27, CI acid blue 40, CI acid blue 41, CI acid blue 45, CI acid blue 62, CI acid blue 80, CI acid blue 129, CI acid blue 138, CI acid blue 215, CI reactive blue 2, CI reactive blue dyes such as blue 4 and CI reactive blue 19; Green dyes such as C. I. acid green 25, C. I. acid green 27, C. I. acid green 28, and C. I. acid green 41.

The chemical structure of the acid dyes (A) exemplified above may be represented as follows.

Basic dyes (B)

The basic dye (B) is a compound capable of ion-bonding by reacting with a sulfonate or carboxylate salt of the acidic dye (A), and specific examples thereof may be represented as follows.

The present invention also relates to

(a) dissolving an acidic dye (A) represented by Formula 1 in deionized water to prepare an acidic dye (A) solution;

(b) dissolving the basic dye (B) of Chemical Formula 2 in deionized water to prepare a basic dye (B) solution;

(c) dropping a basic dye (B) solution into the acid dye (A) solution;

(d) performing filtration after completion of the reaction of step (c) and washing the filtrate with deionized water; And

(E) relates to a method for producing a dye for color filters comprising the step of drying the washed filtrate.

In the preparation method, after the step (a), the step of filtering the acid dye (A) solution may be further performed. Further, after the step (b), the step of filtering the basic dye (B) solution may be further performed.

After the step (c), the completion of the reaction can be confirmed by adding a small amount of HCl or NaOH and stirring to make the aqueous solution transparent.

In the above reaction, the acidic dye (A) and the basic dye (B) may be reacted in equivalent weight equivalents.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited to the following examples and may be variously modified and changed. The scope of the invention will be defined by the technical spirit of the claims below.

Synthetic example  1: Preparation of Basic Dye (B)

In a nitrogen environment, 10 g of aluminum chloride and 5.96 g of oxalyl chloride are added and 80 ml of methylene chloride is refluxed for 20 minutes. Then, 4.5 g of N, N-diethylthiophen-2-amine is slowly added and stirred at room temperature for 2 hours. 3.5 g of N, N-diethylbenzenamine was added thereto, refluxed, and the reaction was confirmed by TLC to obtain a reactant (A). In a nitrogen environment, 0.24 g of Magnesium powder and 7.61 g of iodine are added to 50 ml of THF and sufficiently stirred. Add 4-bromo-N-ethylaniline, reflux until magnesium powder disappears, and slowly add the reactant (A) dissolved in THF. After confirming the completion of the reaction by TLC, after purification by extraction and recrystallization, 5g was dissolved in 30ml of Acetonitrile, 1.08g of Sulfuric acid was added and stirred at 60 ° C for 40 minutes, and then blue basic dye DW-D19-1 through recrystallization. Got.

Synthetic example  2: Preparation of Basic Dye (B)

In a nitrogen environment, 10 g of aluminum chloride and 5.96 g of oxalyl chloride are added and 80 ml of methylene chloride is refluxed for 20 minutes. Then, 4.5 g of N, N-diethylthiophen-2-amine is slowly added and stirred at room temperature for 2 hours. 4.5 g of N, N-Diethyl-1-naphthylamine was added thereto, refluxed, and the reaction was confirmed by TLC to obtain a reactant (A). In a nitrogen environment, 0.24 g of Magnesium powder and 7.61 g of iodine are added to 50 ml of THF and sufficiently stirred. Add 4-bromo-N-ethylaniline, reflux until magnesium powder disappears, and slowly add the reactant (A) dissolved in THF. After confirming the completion of the reaction by TLC, after purification through extraction and recrystallization, 5g was dissolved in 30ml of Acetonitrile, 1.08g of Sulfuric acid was added and stirred at 60 ° C for 40 minutes, and then blue basic dye DW-D19-2 through recrystallization. Got.

Synthetic example  3: Preparation of Basic Dye (B)

Add 10 g of aluminum chloride and 5.96 g of oxalyl chloride in a nitrogen environment, reflux for 20 minutes with 80 ml of methylene chloride, and slowly add 5.5 g of N, N-diethyl-2,3-dihydrobenzo [b] thiophen-6-amine. And stirred at room temperature for 2 hours. 3.5 g of N, N-diethylbenzenamine was added thereto, refluxed, and the reaction was confirmed by TLC to obtain a reactant (A). In a nitrogen environment, 0.24 g of Magnesium powder and 7.61 g of iodine are added to 50 ml of THF and sufficiently stirred. Add 4-bromo-N-ethylaniline, reflux until magnesium powder disappears, and slowly add the reactant (A) dissolved in THF. After confirming the completion of the reaction by TLC, after purification through extraction and recrystallization, 5g was dissolved in 30ml of Acetonitrile, 1.08g of Sulfuric acid was added and stirred at 60 ° C for 40 minutes, and then blue basic dye DW-D19-3 through recrystallization. Got.

Example  1: Preparation of dye for color filter

Anthraquinone-based C. I. acid blue 80 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. The aqueous solution filtered by 0.2 micro filter was dripped at this filtrate, melt | dissolving DW-D19-1 (0.01g) of the synthesis example in deionized water (2 ml).

A small amount of NaOH was added to the solution in which the DW-D19-1 aqueous solution was added dropwise, followed by stirring for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours to remove moisture to obtain a blue D101.

Example  2: Preparation of Dye for Color Filter

Anthraquinone-based C. I. acid blue 80 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. The aqueous solution filtered by 0.2 micro filter was dripped at this filtrate, melt | dissolving DW-D19-2 (0.01g) of the synthesis example in deionized water (2 ml).

A small amount of NaOH was added to the solution in which the DW-D19-2 aqueous solution was added dropwise, followed by stirring for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours to remove moisture to obtain a blue D102.

Example  3: Preparation of Color Filter Dye

Anthraquinone-based C. I. acid blue 80 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. The aqueous solution filtered by 0.2 micro filter was dripped at this filtrate, melt | dissolving DW-D19-3 (0.01g) of the synthesis example in deionized water (2 ml).

A small amount of NaOH was added to the solution in which the DW-D19-3 aqueous solution was added dropwise, followed by stirring for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours to remove moisture to obtain a blue D103.

Comparative Example  1: Preparation of dye for color filter

Anthraquinone C. I. acid blue 40 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. In this filtrate, triaryl methane C. I. basic blue 7 (0.02 g) was dissolved in deionized water (2 ml), and an aqueous solution filtered through a 0.2 micro filter was added dropwise at room temperature.

A small amount of NaOH was added to the solution in which the C. I. basic blue 7 aqueous solution was added dropwise, and stirred for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours to remove moisture to obtain a blue D104.

Comparative Example  2: Preparation of Dye for Color Filter

Anthraquinone-based C. I. acid blue 80 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. In this filtrate, triaryl methane C. I. basic blue 7 (0.01 g) was dissolved in deionized water (1 ml), and an aqueous solution filtered through a 0.2 micro filter was added dropwise at room temperature.

A small amount of NaOH was added to the solution in which the C. I. basic blue 7 aqueous solution was added dropwise, and stirred for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours and water was removed to obtain a blue D105.

Comparative Example  3: Preparation of Color Filter Dye

Azo C. I. direct blue 120 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. In this filtrate, triaryl methane C.I. basic blue 1 (0.02 g) was dissolved in deionized water (2 ml), and an aqueous solution filtered through a 0.2 micro filter was added dropwise.

A small amount of NaOH was added to the solution in which the C. I. basic blue 1 aqueous solution was added dropwise, followed by stirring for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours to remove moisture to obtain a blue D106.

Comparative Example  4: Preparation of Dye for Color Filter

Triarylmethane C. I. acid green 50 (0.01 g) was dissolved in deionized water (1 ml), stirred well, and filtered through a 0.2 micro filter. In this filtrate, triaryl methane C.I. basic green 1 (0.02 g) was dissolved in deionized water (2 ml), and an aqueous solution filtered through a 0.2 micro filter was added dropwise.

A small amount of NaOH was added to the solution in which the aqueous solution of C. I. basic green 1 was added dropwise and stirred for 30 minutes. The completion of the reaction was a time point at which the aqueous solution became transparent.

After completion of the reaction, vacuum filtration was performed and washed with deionized water several times. The reactant remaining on the filter paper was dried at room temperature in a vacuum oven for 24 hours to remove moisture to obtain a blue D107.

Test Example  One.

Solubility and heat resistance of each of the salts synthesized in Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated.

Solubility Assessment

After measuring the solubility of the dyes of Examples 1 to 3 and Comparative Examples 1 to 4 using PGMEA, PGME, EL, DMAc and CHN as a solvent, the results are shown in Table 1 below. In the following table, 10% or more of solubility was expressed as ○, 2% to 10% solubility was represented by Δ, and less than 2% solubility was represented by X.

PGMEA PGME EL DMAc CHN Example 1 Δ ○ ○ ○ ○ Example 2 Δ ○ ○ ○ ○ Example 3 Δ ○ ○ ○ ○ Comparative Example 1 X Δ ○ ○ ○ Comparative Example 2 X Δ ○ ○ ○ Comparative Example 3 X Δ Δ ○ Δ Comparative Example 4 X Δ Δ ○ Δ

PGMEA: Propylene Glycol Monoethyl Ether Acetate

PGME: Propylene Glycol Monoethyl Ether

EL: ethyl lactate

DMAc: dimethylacetamide

CHN: cyclohexanone

≪ Evaluation of heat resistance &

The heat resistance of the dyes of Examples 1 to 3 and Comparative Examples 1 to 4 was measured by TGA using a mass loss rate according to the temperature range, and the results are shown in Table 2 below.

25 ~ 180 ℃ 180 ~ 250 ℃ Total mass reduction Example 1 3% 4% 7% Example 2 8% 4% 12% Example 3 6% 12% 18% Comparative Example 1 10% 12% 22% Comparative Example 2 9% 27% 36% Comparative Example 3 12% 25% 37% Comparative Example 4 11% 28% 39%

As shown in the table above, the solubility and heat resistance of the dyes of Examples 1 to 3 of the present invention was very excellent compared to the dyes of Comparative Examples 1 to 4.

Claims (6)

A dye for a color filter comprising an ionic compound of an anthraquinone acid dye represented by the following formula (A) and a basic dye represented by the following formula (B):
(Formula 1)

In this formula,
m and n are integers of 1 to 3,
X ⁺ is a monovalent to trivalent cation,
R ₁ to R ₆ are each independently hydrogen, hydroxy, amine, -SO ₃ ^- and, -SO ₃ H, a substituted or unsubstituted alkyl of C1 ~ C6 ring, or -NR ^a R ^b, where R ^a and R ^b is each independently Hydrogen, substituted or unsubstituted C1-C6 alkyl, C3-C12 cycloalkyl, C5-C30 aryl, or C5-C30 heteroaryl, wherein C3-C12 cycloalkyl, C5-C30 aryl, and a C5 ~ C30 aliphatic or aromatic ring of the heteroaryl group is a substituted or unsubstituted C1 ~ C20 _{^{alkyl, -SO 3 -, -SO 3 H}} , -CO 2 -, -SO 2 R c And -NR ^d R ^e is unsubstituted or substituted with one or more selected from the group consisting of R ^c , R ^d and R ^e are each independently hydrogen, substituted or unsubstituted C 1 -C 6 alkyl, —CH ₂ ═CH ₂ , —C (═O) R ^f , — (CH 2) o O—SO ₃ ^— , or tria Is a radical group, wherein R ^f is a substituted or unsubstituted C1-C6 alkyl group, the triazine group is unsubstituted or substituted with one or more substituents selected from a phenylamine group substituted with a halogen element and a sulfonate anion, and o is An integer of 1 to 5;
(2)

In the above formula
m and n are integers of 1 to 3,
Y ⁻ is a monovalent to trivalent anion,
R ₀ is benzene or naphthalene,
R _p is thiophene or benzothiophene,
R _{1 ,} R _{2 ,} R _{3 ,} R _{4 ,} R _{5 ,} and R ₆ are each hydrogen, an independently substituted or unsubstituted C 1 -C 6 linear or cyclic alkyl group, or a phenyl group.
The method according to claim 1,
The aryl group in the formula 1 is a color filter dye, characterized in that the phenyl group or naphthalenyl group.
The method according to claim 1,
In Formulas 1 and 2, X ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or Ca ^{2 +} , and Y ⁻ is Cl ⁻ , I ⁻ , Br ⁻ , HSO ₄ ⁻ or OH ⁻ Color filter dye, characterized in that.
The method according to claim 1,
Anthraquinone acid dyes represented by Formula 1 include CI acid blue 25, CI acid blue 27, CI acid blue 40, CI acid blue 41, CI acid blue 45, CI acid blue 62, CI acid blue 80, CI acid blue 129, CI acid blue 138, CI acid blue 215, CI reactive blue 2, CI reactive blue 4, CI reactive blue 19, CI acid green 25, CI acid green 27, CI acid green 28, or CI acid green 41 The dye for color filters.
(a) dissolving an acidic dye (A) represented by Formula 1 in deionized water to prepare an acidic dye (A) solution;
(b) dissolving the basic dye (B) of Formula 2 in deionized water to prepare a basic dye (B) solution;
(c) dropping a basic dye (B) solution into the acid dye (A) solution;
(d) performing filtration after completion of the reaction of step (c) and washing the filtrate with deionized water; And
(E) method for producing a color filter dye comprising the step of drying the washed filtrate:
(Formula 1)

In this formula,
m and n are integers of 1 to 3,
X is a monovalent to trivalent cation,
R ₁ to R ₆ are each independently hydrogen, hydroxy, amine, -SO ₃ ^- and, -SO ₃ H, a substituted or unsubstituted alkyl of C1 ~ C6 ring, or -NR ^a R ^b, where R ^a and R ^b is each independently Hydrogen, substituted or unsubstituted C1-C6 alkyl, C3-C12 cycloalkyl, C5-C30 aryl, or C5-C30 heteroaryl, wherein C3-C12 cycloalkyl, C5-C30 aryl, and a C5 ~ C30 aliphatic or aromatic ring of the heteroaryl group is a substituted or unsubstituted C1 ~ C20 ^{_{alkyl, -SO 3 -, -SO 3 H}} , -CO 2 -, -SO 2 R c And -NR ^d R ^e is unsubstituted or substituted with one or more selected from the group consisting of R ^c , R ^d and R ^e are each independently hydrogen, substituted or unsubstituted C 1 -C 6 alkyl, —CH ₂ ═CH ₂ , —C (═O) R ^f , — (CH 2) o O—SO ₃ ^— , or tria Is a radical group, wherein R ^f is a substituted or unsubstituted C1-C6 alkyl group, the triazine group is unsubstituted or substituted with one or more substituents selected from a phenylamine group substituted with a halogen element and a sulfonate anion, and o is An integer of 1 to 5;
(2)

In the above formula
m and n are integers of 1 to 3,
Y ⁻ is a monovalent to trivalent anion,
R ₀ is benzene or naphthalene,
R _p is thiophene or benzothiophene,
R _{1 ,} R _{2 ,} R _{3 ,} R _{4 ,} R _{5 ,} and R ₆ are each hydrogen, an independently substituted or unsubstituted C 1 -C 6 linear or cyclic alkyl group, or a phenyl group.
The method according to claim 5,
Filtering the acid dye (A) solution after step (a) and filtering the basic dye (B) solution after step (b).