KR20110052156A - Black acid dye composition - Google Patents

Abstract

PURPOSE: A black acid dye composition is provided to make the color of desired concentration using small amount of dye. CONSTITUTION: A black acid dye composition comprises compound of 30~70wt.%, including hydrophilic sulfone amide group, and a water-insoluble compound of 30~70wt.% A high dye absorption rate is obtained by improving the affinity of black acidity dye composition to fiber. A high build up property is maintained for high concentration dyeing.

Description

Black acid dye composition

The present invention relates to a black acid dye composition, in particular a symmetric azo-based metal complex black acid dye composition, at least 30% by weight to 70% by weight of a compound having a hydrophilic sulfonamide group represented by the following [Formula 1], 2] and the water-insoluble compound represented by the following [Formula 3] is a composition of a black acid dye, consisting of a minimum of 30% by weight to a maximum of 70% by weight.

Here, R ₁ is -H, -NHCOCH ₃ , and R ₂ is -NO ₂ , -H, -Cl, -F, -Br, -alkyl group (C ₁ -C ₆ ).

That is, the present invention relates to an environmentally friendly dye capable of high color expression on nylon and polyurethane microfiber nonwovens by mixing a hydrophilic sulfonamide group dye with a hydrophilic group-insoluble black dye by mixing a symmetric azo metal complex black acid dye. will be.

Among the existing azo-based metal dye synthesis methods, the development was carried out based on a 1: 2 symmetrical chroming reaction. Generally, azo-based metal dyes containing sulfonic acid groups have a high affinity for water, and thus, ultrafine nylon and polyurethane When dyeing nonwoven fabrics, all of the dye usage was not colored in the chlorine, so it was difficult to achieve the desired coloration even if a large amount of dyes were used. Has also been a problem.

Since dyes without sulfonic acid groups are not dissolved in water, after dye synthesis is completed, a process of forcibly milling the dye using a dispersant is required, and the milled dye is dispersed in water. Although it is a state, there is a disadvantage in that the spray drying (Spray Dryer) proceeds while consuming a lot of energy to powder it.

Accordingly, in order to reduce the affinity for water and to increase the affinity for the salts, azo-containing metal dyes without sulfonic acid groups were selected, and in order to have solubility that enables dyeing of fungal salts, azo-containing metals with sulfonamide groups 1 : 2 symmetric dyes were used by more than 30% by weight to develop a dye composition capable of high dark color dyeing.

Nylon, polyurethane, and microfibre nonwoven fabrics are generally used in the form of artificial leather for automobiles, clothing, shoes, interiors, and furniture, but are used in various industries. The amount of 絲) is several times more dense than the fabric of ordinary fibers, and the dyeing surface area is very large. Due to this characteristic, a large amount of dye is required, and all of the dyes are not dyed, but a certain amount is drained into the dyeing wastewater. In dyeing companies, production costs such as raw material costs and environmental treatment costs are doubled, There have been a lot of problems.

However, with the development of the present invention in Nile, even a small amount of dye in the polyurethane microfiber non-woven fabric can be expressed in the desired color, and the amount of salt solution waste water is also reduced the environmental impact.

In general, the present invention can be provided by a composition ratio of a sulfonate group removed from a functional group of a metal-containing dye and a sulfonamide group introduced therein and a hydrophilic sulfonic acid group and a sulfonamide group-free metal dye.

With the development of microfiber non-woven dyes, high concentrations of dyes can be achieved with a small amount of dyes, even though a large amount of dyes have not been obtained, and dye use and dyeing wastewater treatment costs can be reduced. Can be.

The black acid dye composition for a high-intensity-expressing microfiber nonwoven fabric according to the present invention is composed of a symmetric azo metal complex dye of the following general formulas (1) to (3).

Here, R ₁ is -H, -NHCOCH ₃ , and R ₂ is -NO ₂ , -H, -Cl, -F, -Br, -alkyl group (C ₁ -C ₆ ).

The black dye composition of the present invention is a hydrophilic dye represented by the formula (1) at least 30% to 70% by weight, the sum of the weight of the water-insoluble dyes represented by the formula (2) and formula (3) is at least 30% by weight to 70% by weight It is composed.

Representative compounds of Formula 1 include the following Formula 1, Structural Formula 2, Structural Formula 3, and Structural Formula 4; Representative compounds of Formula 2 include Structural Formula 5; Representative compounds of Formula 3 There is a compound represented by the formula (6).

Various methods of preparing the dyes used in the present invention are known, but the present inventors have manufactured the following methods.

[Manufacture Reference Example 1]

   [Preparation of Compound 1]

<1> 18.82 parts of 2- (aminohydrobenzene-4-sulfonamide (molecular weight: 188.2) is added to 200 parts of water at room temperature, followed by dispersion for 30 minutes.

<2> 30 parts of hydrochloric acid (35%) is added, and after completion, 100 parts of ice is added and cooled to 0 ° C or lower.

<3> After dissolving 7.6 parts of sodium nitrite (NaNO ₂ ) in 30 parts of water (room temperature), the mixture was stirred for 30 minutes in a solution of the above <2>, the temperature was kept below 0 ° C and stirred for 1 hour. Get (Called "Reactant A")

<4> 15 parts of beta-naphthol (2-Hydroxynaphthalene (molecular weight: 144.2)) is added to 200 parts of water (room temperature), and 5 parts of sodium hydroxide (Flake) is added thereto to complete the solution. Cool to ° C.

<5> Add reactant A of <3> to the solution of <4> and add 50% aqueous solution of sodium hydroxide to maintain pH 9.5 ~ 10, and add ice to maintain the temperature of 5 ~ 10 ℃. Give it.

    After the stock price is maintained at a temperature of about 10 ℃, pH ≒ 10 or more, and stirred for 2 hours or more.

After stirring for 2 hours, the reaction was confirmed, and then neutralized with aqueous hydrochloric acid (35%) to pH ≒ 4 to precipitate crystals. The resultant was filtered using an aspirator to obtain all particles. (Called "Reactant B")

<7> In the other vessel, the reactant B of <6> obtained as a filter cake was added, and about 2.5 times the weight of the filter cake was added to water (room temperature), followed by stirring for about 1 hour.

<8> In another container, 5 parts of chromic acid (Chromic acid, molecular weight 99.99) is added to 250 parts of water (room temperature), 20 parts of formic acid (85%) is added to prepare a green chromformate (Chromformate) dispersion of the above <7>. The mixture was added to the mixture and neutralized with a 50% solution of sodium hydroxide at a pH of about 5 ° C., and the temperature was raised to 105-110 ° C. for 12 hours. After 12 hours, the reaction was confirmed, and when the reaction was completed, the particle state of the reaction solution was confirmed and filtered using an aspirator. At this time, about 20% of sodium chloride (NaCl) may be added to the capacity depending on the particle state. have.

    The obtained filter cake is dried at a temperature of 90 ° C. or lower to obtain a compound of formula 1 which is black in red color. (Yield 85%)

[Manufacture Reference Example 2]

   Preparation of Compound of Structural Formula 2

<1> 18.82 parts of 2-aminohydrobenzene-5-sulfonamide (molecular weight 188.2) is added to 200 parts of water at room temperature, followed by dispersion for 30 minutes.

<2> 30 parts of hydrochloric acid (35%) is added, and after completion, 100 parts of ice is added and cooled to 0 ° C or lower.

<3> After dissolving 7.6 parts of sodium nitrite (NaNO ₂ ) in 30 parts of water (room temperature), the mixture was stirred for 30 minutes in a solution of the above <2>, the temperature was kept below 0 ° C and stirred for 1 hour. Get (Called "Reactant A")

<4> 15 parts of beta-naphthol (2-Hydroxynaphthalene (molecular weight: 144.2)) is added to 200 parts of water (room temperature), and 5 parts of sodium hydroxide (Flake) is added thereto to complete the solution. Cool to ° C.

<5> While adding reactant A of <3> to the solution of <4> above, add 50% aqueous sodium hydroxide solution to maintain pH 9.5 ~ 10, and maintain the temperature of 5 ~ 10 ℃.

    After the stock price is maintained at a temperature of about 10 ℃, pH ≒ 10 or more, and stirred for 2 hours or more.

After stirring for 2 hours, the reaction was confirmed, and then neutralized with an aqueous solution of hydrochloric acid (35%) to pH ≒ 4 to precipitate crystals, and then filtered using an aspirator to obtain all particles. (Called "Reactant B")

<7> In the other vessel, the reactant B of <6> obtained as a filter cake was added, and about 2.5 times the weight of the filter cake was added to water (room temperature), followed by stirring for about 1 hour.

<8> In another container, 5 parts of chromic acid (Chromic acid, molecular weight 99.99) is added to 250 parts of water (room temperature), 20 parts of formic acid (85%) is added to prepare a green chromformate (Chromformate) dispersion of the above <7>. The mixture was added to the mixture and neutralized with a 50% solution of sodium hydroxide at a pH of about 5 ° C., and the temperature was raised to 105-110 ° C. for 12 hours. Check the reaction after 12 hours, and after completion of the reaction, check the particle state of the reaction solution and filter it using an aspirator.If necessary, add 20% sodium chloride (NaCl) to the capacity according to the particle state. can do.

   The obtained filter cake is dried at a temperature of 90 ° C. or less to obtain a compound of formula 2 which is black in red color. (Yield 85%)

[Manufacture Reference Example 3]

   [Preparation of Compound 3]

<1> 18.82 parts of 2-aminohydrobenzene-4-sulfonamide (molecular weight 188.2) is added to 200 parts of water at room temperature, followed by dispersion for 30 minutes.

<2> 30 parts of hydrochloric acid (35%) is added, and after completion, 100 parts of ice is added and cooled to 0 ° C or lower.

<3> After dissolving 7.6 parts of sodium nitrite (NaNO ₂ ) in 30 parts of water (room temperature), the mixture was stirred for 30 minutes in a solution of the above <2>, the temperature was kept below 0 ° C and stirred for 1 hour. Get (Called "Reactant A")

<4> 20.1 parts of 1-acetylamino-7-naphthol (molecular weight 177.2) is added to 200 parts of water (room temperature), and 5 parts of sodium hydroxide (Flake) are added thereto. The temperature of the solution is cooled to 10 ° C by adding ice.

<5> Slowly add reactant A of <3> to the solution of <4> above, add a 50% aqueous solution of sodium hydroxide to maintain pH 9.5 ~ 10, and keep ice at 5 ~ 10 ℃. Add it.

    After the stock price is maintained at a temperature of about 10 ℃, pH ≒ 10 or more, and stirred for 2 hours or more.

After stirring for 2 hours, the reaction was determined by TLC, and then neutralized with hydrochloric acid (35%) to pH ≒ 4 to precipitate crystals. The resultant was filtered using an aspirator to obtain all particles. (Called "Reactant B")

<7> In the other vessel, the reactant B of <6> obtained as a filter cake was added, and about 2.5 times the weight of the filter cake was added to water (room temperature), followed by stirring for about 1 hour.

<8> In another container, 5 parts of chromic acid (Chromic acid, molecular weight 99.99) is added to 250 parts of water (room temperature), 20 parts of formic acid (85%) is added to prepare a green chromformate (Chromformate) dispersion of the above <7>. The mixture was added to the mixture and neutralized with a 50% solution of sodium hydroxide at a pH of about 5 ° C., and the temperature was raised to 105-110 ° C. for 12 hours. Check the reaction after 12 hours, and when the reaction is complete, check the particle state of the reaction solution and filter it using an aspirator.If necessary, add 20% sodium chloride (NaCl) to the capacity according to the particle state. Can be.

    The obtained filter cake is dried at a temperature of 90 ° C. or lower to obtain a compound of formula 3 which is black in green series. (Yield 82%)

[Manufacture Reference Example 4]

   [Preparation of Compound 4]

<1> 18.82 parts of 2-aminohydrobenzene-5-sulfonamide (molecular weight 188.2) is added to 200 parts of water at room temperature, followed by dispersion for 30 minutes.

<2> 30 parts of hydrochloric acid (35%) is added, and after completion, 100 parts of ice is added and cooled to 0 ° C or lower.

<3> After dissolving 7.6 parts of sodium nitrite (NaNO ₂ ) in 30 parts of water (room temperature), the mixture was stirred for 30 minutes in a solution of the above <2>, the temperature was kept below 0 ° C and stirred for 1 hour. Get (Called "Reactant A")

<4> 20.1 parts of 1-acetylamino-7-naphthol (molecular weight 177.2) is added to 200 parts of water (room temperature), and 5 parts of sodium hydroxide (Flake) are added thereto. The temperature of the solution is cooled to 10 ° C by adding ice.

<5> Add reactant A of <3> to solution of <4> and add 50% aqueous sodium hydroxide solution to maintain pH 9.5 ~ 10, and add ice to maintain temperature of 5 ~ 10 ℃. Give it.

    After the stock price is maintained at a temperature of about 10 ℃, pH ≒ 10 or more, and stirred for 2 hours or more.

After stirring for 2 hours, the reaction was determined by TLC, and then neutralized to pH 산 4 with aqueous hydrochloric acid (35%) solution to precipitate crystals. (Called "Reactant B")

<7> In the other vessel, the reactant B of <6> obtained as a filter cake was added, and about 2.5 times the weight of the filter cake was added to water (room temperature), followed by stirring for about 1 hour.

<8> In another container, 5 parts of chromic acid (Chromic acid, molecular weight 99.99) is added to 250 parts of water (room temperature), 20 parts of formic acid (85%) is added to prepare a green chromformate (Chromformate) dispersion of the above <7>. The mixture was added to the mixture and neutralized with a 50% solution of sodium hydroxide at a pH of about 5 ° C., and the temperature was raised to 105-110 ° C. for 12 hours. Check the reaction after 12 hours, and when the reaction is complete, check the particle state of the reaction solution and filter it using an aspirator.If necessary, add 20% sodium chloride (NaCl) to the capacity according to the particle state. Can be.

    The obtained filter cake is dried at a temperature of 90 ° C. or lower to obtain a compound of formula 4 which is black in green series. (Yield 82%)

[Manufacture Reference Example 5]

   [Preparation of Compound 5]

<1> 15.41 parts of 4-nitro-2-amino-phenol (molecular weight 154.1) was added to 200 parts of water at room temperature, followed by dispersion for 30 minutes.

<2> 30 parts of hydrochloric acid (35%) is added, and after completion, 100 parts of ice is added and cooled to 0 ° C or lower.

<3> After dissolving 7.6 parts of sodium nitrite (NaNO ₂ ) in 30 parts of water (room temperature), the mixture was stirred for 30 minutes in a solution of the above <2>, the temperature was kept below 0 ° C and stirred for 1 hour. Get (Called "Reactant A")

<4> 15 parts of beta-naphthol (2-Hydroxynaphthalene (molecular weight: 144.2)) is added to 200 parts of water (room temperature), and 5 parts of sodium hydroxide (Flake) is added thereto to complete the solution. Cool to ° C.

<5> While adding reactant A of <3> to solution of <4> above, add 50% aqueous sodium hydroxide solution to maintain pH 9.5 ~ 10, and maintain temperature of 5 ~ 10 ℃. After the stock price is maintained at a temperature of about 10 ℃, pH ≒ 10 or more, and stirred for 2 hours or more.

After stirring for 2 hours, the reaction was confirmed, and then neutralized with aqueous hydrochloric acid (35%) to pH ≒ 4 to precipitate crystals. The resultant was filtered using an aspirator to obtain all particles. (Called "Reactant B")

<7> The reactant B of <6> obtained as a filter cake was placed in another container, and water (room temperature) was added about 2.5 times the weight of the filter cake, followed by stirring for about 1 hour.

<8> In another container, 5 parts of chromic acid (Chromic acid, molecular weight 99.99) is added to 250 parts of water (room temperature), 20 parts of formic acid (85%) is added to prepare a green chromformate (Chromformate) dispersion of the above <7>. The mixture was added to the mixture and neutralized with a 50% solution of sodium hydroxide at a pH of about 5 ° C., and the temperature was raised to 105-110 ° C. for 12 hours. Check the reaction after 12 hours, and when the reaction is complete, check the particle state of the reaction solution and filter it using an aspirator.If necessary, add 20% sodium chloride (NaCl) to the capacity according to the particle state. Can be.

    The obtained filter cake is dried at a temperature of 90 ° C. or lower to obtain a compound of formula 5. (Yield 88%)

[Manufacture Reference Example 6]

   Preparation of Compound 6

<1> 15.41 parts of 5-nitro-2-amino-phenol (molecular weight 154.1) was added to 100 parts of water at 60 ° C., followed by dispersion for 30 minutes.

<2> 40 parts of hydrochloric acid (35%) is added, and after completion, 200 parts of ice are added and cooled to 0 ° C or lower.

<3> After dissolving 7.6 parts of sodium nitrite (NaNO ₂ ) in 30 parts of water (room temperature), the mixture was stirred for 30 minutes in a solution of the above <2>, the temperature was kept below 0 ° C and stirred for 1 hour. Get (Called "Reactant A")

<4> 15 parts of beta-naphthol (2-Hydroxynaphthalene (molecular weight: 144.2)) is added to 200 parts of water (room temperature), and 5 parts of sodium hydroxide (Flake) is added thereto to complete the solution. Cool to ° C.

<5> While adding reactant A of <3> to solution of <4> above, add 50% aqueous sodium hydroxide solution to maintain pH 9.5 ~ 10, and maintain temperature of 5 ~ 10 ℃. After the stock price is maintained at a temperature of about 10 ℃, pH ≒ 10 or more, and stirred for 2 hours or more.

After stirring for 2 hours, the reaction was confirmed, and then neutralized with aqueous hydrochloric acid (35%) to pH ≒ 4 to precipitate crystals. The resultant was filtered using an aspirator to obtain all particles. (Called "Reactant B")

<7> The reactant B of <6> obtained as a filter cake was placed in another container, and water (room temperature) was added about 2.5 times the weight of the filter cake, followed by stirring for 1 hour.

<8> In another container, 5 parts of chromic acid (Chromic acid, molecular weight 99.99) is added to 250 parts of water (room temperature), 20 parts of formic acid (85%) is added to prepare a green chromformate (Chromformate) dispersion of the above <7>. The mixture was added to the mixture and neutralized with a 50% solution of sodium hydroxide at a pH of about 5 ° C., and the temperature was raised to 105-110 ° C. for 12 hours. Check the reaction after 12 hours, and when the reaction is complete, check the particle state of the reaction solution and filter it using an aspirator.If necessary, add 20% sodium chloride (NaCl) to the capacity according to the particle state. Can be.

    The obtained filter cake is dried at a temperature of 90 ° C. or lower to obtain a compound of the old breakfast 6. (83% yield)

The dyes of Formula 1 (Formula 1, Structural Formula 2, Structural Formula 3, Structural Formula 4) and Formula 2 (Formula 5) and Formula 3 (Formula 6) prepared according to the Preparation Reference Examples 1 to 6 as described above Mixing at a constant ratio yields the final dye.

That is, the black dye composition of the present invention is composed of 30 to 70% by weight of the compound of formula 1, 70 to 30% by weight of the sum of the compounds of formula (2) and formula (3).

Furthermore, dyeing of general dyes does not dye up to 15% or more of dyes on the weight of fiber (dye on the weight of fiber), but the dye composition of the present invention is a general acid dye. Can be as deep as 25%, which is difficult to achieve.

Dyeing method mainly uses dyeing method, dyeing aid such as pH adjuster, leveling agent, penetrant, etc., and general nylon dyeing method is applied.

Each dyeing aid contains about 5 ~ 10% of powder type dispersant and about 5% pH adjuster to dye weight. Add 1% of homogenizer and penetrant to make salt solution, and make salt solution. After neutralizing the 4 to 5, the temperature is increased by 1 ℃ per minute at room temperature up to 99 ℃, give a leveling time of about 1 ~ 1.5 hours at 99 ℃.

After dyeing, wash with lukewarm water several times, add about 1 ~ 5% of the fixing agent for dyeing dye, and neutralize it with pH ≒ 4 ~ 5 using acetic acid, and then at 80 ℃ Fix it for about 1 hour.

Dyeing in this process enables high-density coloration to the aforementioned nylon and polyurethane microfiber nonwoven fabrics, and it is possible to make environmentally friendly dyes that reduce the amount of dye residue in the waste water generated during dyeing.

Next, an Example of this invention composition is given and this invention is demonstrated again concretely.

Example 1

A total of 100 parts of the dye mixture is made from the sum of 40 parts of the dye of formula 1, 30 parts of the dye of formula 5 and 30 parts of the dye of formula 6. In addition, Dywell-500 dispersant, which corresponds to 10% of the total weight of the dye mixture, 5% of soda ash, and 5% of forget-me-not, makes the whole homogeneous, resulting in excellent build-up. High concentration dyeing is possible, and the dyeing waste water of the red-based black (reddish black) acid dye composition of the present invention is made.

[Example 2]

A total of 100 parts of the dye mixture is made from the sum of 40 parts of the dye of formula 2, 30 parts of the dye of formula 5 and 30 parts of the dye of formula 6. Here, Dywell-500 dispersant, which is 10% of the total weight of the dye mixture, 5% of soda ash and 40% of forget-me-not, makes the whole homogeneous, so that the build-up is excellent. High concentration dyeing is possible, and the dyeing waste water of the red-based black (reddish black) acid dye composition of the present invention is made.

Example 3

A total of 100 parts of the dye mixture is made from the sum of 40 parts of the dye of formula 3, 30 parts of the dye of formula 5 and 30 parts of the dye of formula 6. Here, Dywell-500 dispersant, which is 10% of the total weight of the dye mixture, 5% of soda ash and 50% of forget-me-not, makes the whole homogeneous and excellent build-up. In addition, high-density dyeing is possible, and a greenish black acid dye composition having less dyeing wastewater is produced.

Example 4

A total of 100 parts of the dye mixture is made from the sum of 40 parts of the dye of formula 4, 30 parts of the dye of formula 5 and 30 parts of the dye of formula 6. Here, Dywell-500 dispersant, which is 10% of the total weight of the dye mixture, 5% of soda ash and 50% of forget-me-not, makes the whole homogeneous and excellent build-up. It is possible to make a higher concentration of dye, and to produce a darker greenish black acid dye composition with less dyeing waste water.

Dye of the black acid dye composition composed of the above embodiments, compared to the conventional black acid dye, can be high color, excellent build-up (dye), excellent dye adsorption rate in the dye wastewater during dyeing It is an environmentally friendly dye with a small residual amount.

Washing and wet friction fastness is more than 3 grades, water and dry friction fastness, daylight fastness are all 3 ~ 4 grade or more, satisfies the properties of ordinary metal dyes.

The comparative example of the dye composition of Examples 1-4 of this invention, and the conventional acid dye as follows is illustrated.

Comparative Example 1

In the dye composition of Example 1 of the present invention and general symmetrical and asymmetrical metal-containing dyes, a sulfonic acid group having an asymmetric type Acid Black 107 and a sulfonic acid group and a sulfonic amide group having a symmetric type Acid Black 63 were used for the nylon polyurethane microfiber nonwoven fabric. By dyeing, the dye adsorption rate was measured, shown in Table 1 and FIG.

And, the dye composition of Example 1, acid black 172 having a sulfonic acid group, and a residual photo of the staining bath of acid black 63 without a sulfonic acid group and a sulfonamide group are shown in FIG. 2.

Table 1 Comparison of dyeing properties for each dye of Comparative Example 1

In Table 1, the dye adsorption rate was measured by the following method.

-Dye adsorption rate (2% dyeing, Dye-O-Meter, bath ratio 1: 30)

In the residual bath experiment of FIG. 2, the dye composition of Example 1 according to the present invention, Acid Black 172 with sulfonic acid group, and Acid Black 63 without sulfonic acid group and sulfonamide group, respectively, were 5% and 10% of OWF. %, 15%, 20%, 25% were stained, and the remaining dyeing bath after dyeing was compared by photographs.

As can be seen in Table 1 and FIGS. 1 and 2, it can be seen that the dye adsorption rate of the present invention is higher than that of the two dyes of the comparative example, and even when the same amount of dye is used, a much higher color can be realized. Also, even in the saline wastewater, since the remaining amount of the dye is small, the dyeing wastewater treatment cost can be reduced, and it can be seen that it is much more economical than the existing azo-based metal dyes.

1 is a graph showing the dye adsorption rate by dyeing a nylon, polyurethane microfiber nonwoven fabric with a dye composition of Example 1 according to the present invention and Acid Black 107 and Acid Black 63 according to Comparative Example 1.

Figure 2 is a dye composition of Example 1 according to the present invention and Acid Black 172 and Acid Black 63 according to Comparative Example 1, respectively OWF (use of dye to the weight of the salt) 5%, 10%, 15%, 20%, It is dyed at 25% and the remaining dyeing bath comparison picture after dyeing.

Claims (2)

In the black acid dye composition, at least 30% by weight to at most 70% by weight of the compound having a hydrophilic sulfonamide group represented by the following formula (1), and at least 30% by weight to the maximum weight of the water-insoluble compound represented by the following formulas (2) and (3): Black acid dye composition, consisting of 70% by weight.

Here, R ₁ is -H, -NHCOCH ₃ , and R ₂ is -NO ₂ , -H, -Cl, -F, -Br, -alkyl group (C ₁ -C ₆ ). According to claim 1, wherein the compound of Formula 1 is a compound selected from compounds of Formula 1, Formula 2, Formula 3, Formula 4, the compound of Formula 2 is a compound of Formula 5, The compound of Black acid dye composition is the compound of formula 6.

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