KR20000072392A - New balck and navy blue disperse dye composition - Google Patents

Abstract

PURPOSE: A black or navy blue disperse dye composition compounded with three blue azo dyes, one red azo dye, one yellow dye and one brown azo dye in an optimum ratio is provided which has excellent heat migration, a characteristic by which an unexhausted dye is easily washed from the surface of fibers by a detergent and high wet fastness and gas fastness and exhibits low metamerism. CONSTITUTION: The disperse dye composition comprises 10 to 30% by weight of a blue azo dye compound of formula 4, 10 to 20% by weight of a blue azo dye compound of formula 5, 10 to 30% by weight of a blue azo dye compound of formula 6, 10 to 20% by weight of a red azo dye compound of formula 7, 10 to 30% by weight of a yellow azo dye compound of formula 8 and 2 to 10% by weight of a brown azo dye compound of formula 9. In formula, R is H, methyl or acetylamino, Y is methoxy or ethoxy, A and B are the same or different acetoxy or oxopropoxy, R1 and R2 are H or halogen.

Description

New balck and navy blue disperse dye composition

The present invention relates to novel black and navy blue dispersion dye compositions. More specifically, the present invention relates to novel black and navy blue disperse dye compositions having high wet fastness and excellent gas fastness when dyeing cellulose diacetate or triacetate fibers, and without metamerism.

Existing black and navy blue disperse dyes are banned by Eco-tex, a European textile label, and also have low wet fastness when dyeing cellulose diacetate or triacetate fiber and metamerism. This problem is caused.

In particular, the conventional dispersible azo dyes represented by the following Chemical Formulas 1, 2, and 3, due to the problem of irritation to human skin, from the late 1990s, the European eco-tex label is conventionally prohibited from using the dye, the present invention Dye composition is a harmless dye that is not included in the ecotex regulation.

The black and navy blue disperse dyes most commonly used for the dyeing of acetate fibers include a blue azo dye of the following formula (1), a red azo dye of the following formula (2) and a yellow azo dye of the following formula (Lumacel navy blue S- GF and black S-GF).

[Formula 1]

[Formula 2]

[Formula 3]

These disperse dyes are skin irritant dyes, and also have low wet fastnesses such as washing, water and sweat fastness, and there is a big problem (metamerism) in which the visible color changes seriously as the light source changes. Since the 1990s, the trend of the global textile market demands much improved wet fastness than conventional dyes, and thus, navy blue and black dyes using the composition dyes of Formulas 1 to 3 are difficult to use any more, and thus new dyes having excellent fastness Development has been urgently needed. This low wet fastness is due to the inherent chemical properties of conventional dyes, and the dyes have disadvantages of poor heat transfer due to chemical structure, and strong other fiber contamination such as nylon when washing or sweating.

Therefore, the present inventors have studied the correlation between the chemical structure of azo dye compound and acetate fiber dyeing property and wet fastness. As a result, the chemical structure is superior to thermal dyes compared to the conventional dispersion dyes, and the undyed dyes have a cleaning process. He developed a heterocycle-based blue azo dye with excellent cleaning properties and a red and orange azo dye with excellent thermal dyeing ability.These dyes are formulated in optimal proportions to have excellent compatibility. New black and navy blue azo dyes with the desired high wet fastnesses have been developed.

The present invention provides a blue azo dye of formula (4), a blue azo dye of formula (5), a blue azo dye of formula (6), a red azo dye of formula (7), yellow of formula (8) The present invention relates to a novel black and navy blue dye composition containing an azo dye and a brown azo dye of the formula (9).

[Formula 4]

[Eating above. X is hydrogen, methyl or acetylamino group, Y is methoxy or ethoxy and A and B are the same or different acetoxy or oxopropoxy groups],

[Formula 5]

[Wherein X is hydrogen, methyl or acetylamino group, Y is hydrogen, methoxy or ethoxy and A and B are the same or different acetoxy or oxopropoxy groups],

[Formula 6]

[Wherein X is hydrogen, methyl or acetylamino group, Y is hydrogen, methoxy or ethoxy and A and B are the same or different hydrogen, acetoxy, methoxycarbonyl or ethoxycarbonyl group],

[Formula 7]

[Wherein R ¹ and R ² are the same or different hydrogen, cyano or halogen groups, A and B are the same or different hydrogen or acetoxy groups],

[Formula 8]

[Wherein R ¹ and R ² are the same or different hydrogen or halogen groups, A and B are the same or different cyano or acetoxy groups],

[Formula 9]

[Wherein R ¹ and R ² are the same or different hydrogen or halogen groups, A and B are the same or different hydroxy or acetoxy groups],

The black dye composition according to the present invention is 10 to 30% by weight of the blue azo dye of Formula 4, 10 to 20% by weight of the blue azo dye of Formula 5, 10 to 30% by weight of the blue azo dye of Formula 6, red azo dye of Formula 7 It is preferable to contain 10-20 weight%, 10-30 weight% of yellow azo dyes of Formula 8, and 2-10 weight% of brown azo dyes of Formula 9.

Navy blue dye composition according to the present invention is 15 to 40% by weight of the blue azo dye of Formula 4, 10 to 20% by weight of the blue azo dye of Formula 5, 15 to 40% by weight of the blue azo dye of Formula 6, red azo of Formula 7 It is preferable to contain 5-10% of dye, 10-20% of yellow azo dye of formula (8), and 0-10% of brown azo dye of formula (9).

The black and navy blue dyes according to the invention do not contain composition dyes regulated by Ecotex, and therefore are particularly suitable dyes for the European market. In the dye, as well as wet fastness is important dyeing of acetate fibers, conventional dyes used a low energy type dye having a low chemical structure of the dye so that the dyeability, but these dyes had a disadvantage of low wet fastness. On the other hand, when a high-energy dye having a large molecular structure of dye having excellent wet fastness is used, the dyeability to acetate fibers is remarkably inferior. However, in the present invention, a mixture of heterocycle blue azo dyes such as Chemical Formulas 4 to 6 is mixed, and high energy azo dyes such as Chemical Formulas 7 to 9 compatible with these dyes are mixed in an appropriate ratio to give acetate fiber dyeing properties. Prepare navy blue and black dyes that can be significantly enhanced. According to the dye chemical theory, it is known that the use of a mixture of different dyes mainly depends on the physical properties of each of the composition dyes. However, in the present invention, the mixing technology of the heterocycle-based blue azo dyes has a decisive effect on acetate fiber dyeability. Is based on discovery. In terms of wet fastness, heterocycle-based blue azo dyes and high-energy azo dyes have better thermal dyeing than low-energy azo dyes used in conventional dyes, and washability of undyed dyes remaining on the fiber surface after dyeing. This is excellent and ultimately results in significantly improved wet fastness. Metamerism, another problem of conventional dyes, is a phenomenon caused by different energy curves for each light source of the composition dye, and the azo dyes of Formulas 4 to 9 used in the present invention have a very energy curve for a light source. As they have similar properties, they are characterized by excellent physical properties without such metamerism.

The present invention also has excellent wet fastness and low metamerism by dyeing black and navy blue dyes prepared by blending the azo dye compounds of Formulas 4 to 9 in a suitable proportion to acetate fibers or acetate fibers and polyester and blended fibers. It provides a dyeing method characterized in that the obtained.

The blue azo dye compound of Formula 4 used in the dye composition of the present invention is prepared by diazo and coupling reaction of a diazo body of Formula 10 and a coupler body of Formula 11 below.

[Formula 10]

[Formula 11]

In the above formula,

X, Y, A, B are the same as in the above-mentioned formula (4).

The blue azo dye compound of Chemical Formula 5 is prepared by diazo and coupling reaction between a diazo body of Formula 12 and a coupler body of Formula 11 below.

[Formula 12]

The blue azo dye compound of Chemical Formula 6 is prepared by diazo and coupling reaction between a diazo body of Formula 13 and a coupler body of Formula 11 below.

[Formula 13]

As the azo dye compounds of Formulas 7 to 9, commercially available dyes were used.

The pure dye compound obtained as described above is finely pulverized in dynomil so that dye particles having a particle size of less than 1 μm are 90% or more, using a dispersant in which naphthalene sulfonic acid / formaldehyde condensate and lignin sulfonic acid are mixed as a medium. It is prepared in a dispersion of and then dried with a spray dryer to obtain a dye in powder form. The final black and navy blue dyes are prepared using the blue, red, brown and yellow dyes in powder form in the mixing ratios shown in Table 1 for direct printing and dyeing.

Table 1. Mixing ratio of composition dyes

Formula 4 (%) Formula 5 (%) Formula 6 (%) Formula 7 (%) Formula 8 (%) Formula 9 (%) Black Dye 10-30 10-20 10-30 10-20 10-30 2 ~ 10 Navy Blue Dye 15-40 10-20 15-40 5-10 10-20 0-10

The black and navy blue dyes according to the present invention were washed with water and sweat after dyeing to acetate fibers, and compared with the results. The results were significantly better than the conventional black and navy blue dyes of Chemical Formulas 1 to 3. This is because the blue, red, yellow, and brown composition dyes having a chemical structure as shown in Table 2 below have inherent excellent wet fastnesses (Table 5), and thus new black and navy blue dyes prepared by combining these composition dyes. The fastness of the is greatly improved. In particular, the blue azo dyes studied by the present inventors have a chemical structure designed to have excellent wet fastness during dyeing processing.

For example, the dyes of Formula 4 and Chemical Formula 5 have inherent color strengths stronger than those of conventional dyes, so that a desired color density can be obtained even with a small amount of dyes. Alternatively, when two kinds of blue dyes are used, the dyeing rate is significantly increased, and the wet fastness is improved compared to the conventional dyes used in excess in order to obtain a desired dyeing concentration.

In addition, from the chemical point of view, the wet fastness is improved because the dye-free dye on the surface of the fiber by the cleaning agent is excellent in the cleaning process after dyeing. Washing fastness (AATCC 2A method), sweat fastness (AATC 15-1989 method) and water fastness of new black and navy blue dyes developed by commercially mixing blue, red, yellow and brown azo dyes having the above-mentioned chemical properties (Max & Spence C6 method) is grade 4 or higher (see Tables 6 and 7), and a significant improvement in quality is achieved when comparing the level of color fastness of the black and navy blue dyes of the general formulas (1) to (3). . Therefore, the black and navy blue dyes according to the present invention satisfy the quality level of the European market requiring high-quality clothing products (washing, sweat and water fastness level 4 or higher).

Wet fastness (particularly washing and water fastness) was not important until the mid-1990s, since diacetate fibers were mainly used in lining papers for formal clothing and were only dry-cleaned. However, in recent years, the use of acetate fibers for clothing fabrics with a good feel as the teaching materials used by mixing various different fibers as clothing materials has grown rapidly. Therefore, washing with water for washing using a domestic washing machine is possible. And the level of demand for water fastness is greatly increased, it is impossible to use the conventional dye, the above-mentioned fastness is weak. Therefore, the novel dyes of the present invention are considered to be actively in line with this global market change.

Another problem with conventional dyes is that metamerism is a severe color difference depending on the light source. For example, it appears to be different colors indoors and outdoors. The novel dyes of the present invention are designed to have similar energy absorption curves for different light sources (daylight, fluorescent UV, etc.) of each of the composition dyes to completely solve the above-mentioned disadvantages.

Chemical structures of representative dye compounds of Formulas 4 to 9 used in the dye composition of the present invention are shown in Table 2 below.

Table 2. Chemical Structure of Dye Compounds of Formulas 4-9

Hereinafter, although this invention is demonstrated concretely based on a manufacture example and an Example, the technical scope of this invention is not limited to these. The term "part" as used in Preparation Examples and Examples means parts by weight.

Preparation Example 1

25.7 parts of sodium nitrite were slowly added to 200 parts of concentrated sulfuric acid (concentration 98%) at room temperature, and it stirred for 1 hour, maintaining 65-70 degreeC. After the reaction is cooled to 10 ° C. or lower, 200 parts of glacial acetic acid and 50 parts of propionic acid are slowly added at the same temperature. While maintaining the same temperature, 50 parts of the diazo-body 2-amino-5-nitrothiazole are slowly added for about 1 hour. Stir at 5-10 degreeC for 1 hour, and complete the diazotization reaction. In a mixed solution of 1,200 parts of water, 500 parts of ice and 70 parts of glacial acetic acid, 105 parts of the coupler chain N, N- (β-diacetoxyethyl) -m-aminoacetanilide were completely dissolved and then cooled to below 10 ° C. The diazo compound is added at 0 to 10 DEG C for about 1 hour, and stirred at the same temperature for 1 hour. Dilute (10%) caustic soda at a temperature below 10 ° C and slowly adjust the pH of the reaction to 3-4, and then filter, wash and dry the fish dye to obtain 133 parts (yield: 85%) of pure dye compound.

100 parts of pure dye (Formula 4-1) is added to 50 parts of naphthalene sulfonic acid / formaldehyde condensation type dispersion, 50 parts of lignin sulfonic acid-based dispersant and 1,000 parts of water, and pulverized so that 90% or more of the dye particles are less than 1 μm. Dye dispersion was prepared and spray dried to obtain the final blue dispersion dye.

Preparation Examples 2 to 8

A blue dye compound (Formula 4-2 to 4-8) shown in Table 2 was prepared in the same manner as in Preparation Example 1.

Preparation Example 9

24 parts of sodium nitrite was slowly added to 240 parts of concentrated sulfuric acid (concentration 98%) at room temperature and stirred for 1 hour while maintaining 65 to 70 ° C. After the reaction is cooled to 10 ° C. or lower, 160 parts of glacial acetic acid and 40 parts of propionic acid are slowly added at the same temperature. While maintaining the same temperature, 60 parts of the diazo body 2-amino-3,5-dinitrothiophene were slowly added for about 1 hour. Stir at 5-10 degreeC for 1 hour, and complete the diazotization reaction. After mixing 1,000 parts of water, 400 parts of ice and 60 parts of acetic acid, 80 parts of N, N- (β-diacetoxyethyl) aniline, a coupler body, are completely dissolved, and then cooled to below 10 ° C. The diazo compound was joined at 0 to 10 ° C. for about 1 hour, stirred at the same temperature for 1 hour, and then the resulting dye was filtered, washed with water and dried to obtain 115 parts of pure dye compound (Formula 5-1) (yield: 78%). Get)

50 parts of pure dyes (Formula 5-1) are added to part 25 of naphthalene sulfonic acid / formaldehyde condensation type dispersion, 25 parts of lignin sulfonic acid-based dispersant and 500 parts of water, and pulverized so that at least 90% of the dye particles are less than 1 μm. Dye dispersions were prepared and then spray dried to obtain the final blue dispersion dye.

Preparation Examples 10 to 18

A blue dye compound (Formula 5-2 to 5-10) shown in Table 2 was prepared in the same manner as in Preparation Example 9.

Preparation Example 19

39 parts of sodium nitrite were slowly added to 400 parts of concentrated sulfuric acid (concentration 98%) at room temperature, and it stirred for 1 hour, maintaining 65-70 degreeC. After the reaction was cooled to 10 ° C. or lower, 100 parts of the diazo compound 7-amino-5-nitrobenzoisothiazole were slowly added at about the same temperature for about 1 hour. Stir at 5-10 degreeC for 1 hour, and complete the diazotization reaction. In a solution of 1,500 parts of water, 600 parts of ice and 120 parts of acetic acid, 73 parts of N, N- (diethyl) aniline, a coupler chain, were completely dissolved and then cooled to below 10 ° C. The diazo compound was slowly added for 1 hour while maintaining 0 to 10 ° C, and stirred at the same temperature for 1 hour. Dilute (10%) aqueous solution of caustic soda at less than 10 ℃ to adjust pH of reactant to 3 ~ 4, and then filter, wash, and dry the resulting dye to prepare 160 parts of pure blue dye compound (Formula 6-1) Yield: 88%).

100 parts of pure blue dyes (Formula 6-1) are added to 50 parts of naphthalene sulfonic acid / formaldehyde condensation type dispersant, 50 parts of lignin sulfonic acid type dispersant and 1,000 parts of water, and pulverized so that 90% or more of the dye particles are less than 1 μm. Dye dispersions were prepared and then spray dried to obtain the final blue dispersion dye.

Preparation Example 20-28

A blue dye compound as described in Table 2 in a similar manner to Preparation Example 19

6-2 to 6-10).

Preparation Example 29

50 parts of pure red dye (Formula 7-1) is added to 25 parts of naphthalene sulfonic acid / formaldehyde condensation type dispersant, 25 parts of lignin sulfonic acid-based dispersant and 500 parts of water, and pulverized so that 90% or more of the dye particles are less than 1 μm. Dye dispersion was prepared and then spray dried to obtain the final red dispersion dye.

Preparation Examples 30 to 42

The dye compounds (Formula 7-2) to 9-5) shown in Table 2 were prepared by analogy to the method of Preparation Example 29.

Example 1

5 parts of the blue dye of the formula 4-1 obtained in Preparation Example 1, 8 parts of the blue dye of the formula 5-1 obtained in Preparation Example 9, 15 parts of the blue dye of the formula 6-1 obtained in Preparation Example 19, Preparation Example 29 5 parts of the red dye of Formula 7-1, 15 parts of the yellow dye of Formula 8-1 and 2 parts of the brown dye of Formula 9-1 were mixed and stirred at room temperature for 1 hour to obtain a uniformly mixed new black dye 1. When dyed to 100% diacetate fiber (dyeing temperature 88 ℃) as shown in Table 6 excellent washing, water and sweat fastness.

Examples 2-14

In the same manner as in Example 1, a black dye compound (black dye 2 to black dye 14) shown in Table 4 was prepared. At this time, the formula and the mixing ratio of each composition dye are shown in Table 3.

Table 3. Chemical formulas and amounts used of the composition dyes used to prepare the black dyes of the present invention

Example 15

In 10 parts of the blue dye of Formula 4-1 obtained in Preparation Example 1, 8 parts of the blue dye of Formula 5-1 obtained in Preparation Example 9, and 15 parts of the blue dye of Formula 6-1 obtained in Preparation Example 19 5 parts of the red dye of Formula 7-1, 7 parts of the yellow dye of Formula 8-1, and 2 parts of the brown dye of Formula 9-1 were mixed and stirred at room temperature for 1 hour to obtain a uniformly mixed navy blue dye. When dyeing% diacetate fiber (dyeing temperature of 88 ℃) it shows excellent washing, water and sweat fastness as shown in Table 7.

Examples 16-22

The navy blue dye compound (navy blue dye 2 to navy blue dye 8) shown in Table 5 was prepared in the same manner as in Example 15. At this time, the formula and mixing ratio of each composition dye is shown in Table 4.

Table 4. Amount of Composition Dye Used to Prepare Navy Blue Dyestuff of the Present Invention

Example number Composition dyes Example number Composition dyes Example 16 Blue 4-2 10 Blue Blue 5-2 8 Blue Blue 6-2 18 Blue Red 7-4 4 Blue Yellow 8-1 10 Blue Brown 9-2 1 Example 17 Blue 4-3 15 Blue Blue 5-3 10 Blue Blue 6-3 21 Blue Red 7-3 6 Blue Yellow 8-5 13 Blue Brown 9-3 2 Example 18 Blue 4-4 12 Blue Blue 56 8 Blue Blue 6-6 19 Blue Red 7-4 7 Blue Yellow 8-5 10 Blue Brown 9-4 2 Example 19 Blue 4-5 15 Light blue 5-1 11 Light blue 6-2 23 Light red 7-3 9 Light yellow 8-3 11 Light brown 9-4 2 Example 20 Blue 4-6 17 Blue Blue 5-7 12 Blue Blue 6-5 18 Blue Red 7-3 8 Blue Yellow 8-4 10 Blue Brown 9-1 3 Example 21 Blue 4-7 16 Blue Blue 5-2 10 Blue Blue 6-8 22 Blue Red 7-2 7 Blue Yellow 8-3 11 Blue Brown 9-4 2 Example 22 ‘Blue 4-8’16 Violet Blue 5-10 10 Violet Blue 6-8 19 Iron Red 7-2 7 Orange Yellow 8-5 10 Orange Brown 9-3

Color fastness test example

Washing fastness (AATCC 2A method) of the dyeing of the dyeing as described above is polymat (made by AHIBA), water fastness (M & S C6 method) is oven at 37 ℃ (product made by HERAEUS), sweat fastness (AATCC 15-1989) is It measured, respectively (made by HERAEUS). The fastness test results are shown in Tables 5, 6 and 7 below.

Table 5. Main Color Fastness of Dyes of Chemical Formulas 4-9

Dye Type Color fastness to washing (AATCC2A) Water fastness (M & S C6) Nylon pollution Acetate pollution Nylon pollution Acetate pollution Formula 4-1 Formula 4-2 Formula 4-3 Formula 4-4 Formula 4-5 Formula 4-6 Formula 4-7 Formula 4-8 Formula 5-1 Formula 5-2 Formula 5-3 Formula 5-4 Formula 5 -5 Formula 5-6 Formula 5-7 Formula 5-8 Formula 5-9 Formula 5-10 Formula 6-1 Formula 6-2 Formula 6-3 Formula 6-4 Formula 6-5 Formula 6-6 Formula 6-7 Chemical Formula 6-8 Chemical Formula 6-9 Chemical Formula 6-10 44-5444-54444-54-5444-544-54-54-54-5444-544444-544 444-54-5444-54-54-54-544-54-5444-54-544444-54-54444-54 4-544-54-544-54-54-5444-54-54-544-54-54-5444-54-54444-544 4-54-55544-54-554-54-54-554-54-54-54-554-54-54-554-54-544-54-544-5

Formula 7-1 Formula 7-2 Formula 7-3 Formula 7-4 Formula 8-1 Formula 8-2 Formula 8-3 Formula 8-4 Formula 8-5 Formula 9-1 Formula 9-2 Formula 9-3 Formula 9 Formula 9-5 43-444443-44-543-44444 3-4444-54-53-44443-43-44-544-5 443-44443-4443-44444 444443-444-54-5444-544-5

Table 6. Main fastness of black dyes of the present invention

* Existing Dye: Black Dye of Chemical Formula 1 ~ 3

Dye Type Sweat fastness (AATCC 15-1989) Nylon pollution Acetate pollution Conventional dyes New dyes 1 New dyes 2 New dyes 3 New dyes 4 New dyes 5 New dyes 6 New dyes 7 New dyes 8 New dyes 9 New dyes 10 New dyes 11 New dyes 12 New dyes 13 New dyes 14 2444-544-5444-5444-5444-5 24-5444-54-54-54-544-5444-544-5

Table 7. Main fastness of navy blue dye of the present invention

Dye Type Color fastness to washing (AATCC 2A) Water fastness (M & S C6) Nylon pollution Acetate pollution Nylon pollution Acetate pollution Conventional dyes New dyes 1 New dyes 2 New dyes 3 New dyes 4 New dyes 5 New dyes 6 New dyes 7 New dyes 8 244-54444-544-5 24-54-544-544-54-54 244-54-54-544-544-5 2-34-54-544-5454-54

* Existing dyes: Navy blue dyes of the formula

Dye Type Sweat fastness (AATCC 15-1989) Nylon pollution Acetate pollution Conventional dyes New dyes 1 New dyes 2 New dyes 3 New dyes 4 New dyes 5 New dyes 6 New dyes 7 New dyes 8 2444-544-54-544-5 2444-544-54-544-5

As described above, the black and navy blue dye compositions according to the present invention have superior heat dissipation properties in terms of chemical structure as compared to conventional dispersion dyes, and further, the undyed dyes are effectively washed from the fiber surface by a detergent used during the cleaning process. It has high wet fastness and good gas fastness and low metamerism.

Claims (6)

Blue azo dyes of formula (4), Blue azo dyes of formula (5), Blue azo dyes of formula (6), Red azo dyes of formula (7), Yellow azo dyes of formula (8), and New black and navy blue dye composition for dyeing containing a brown azo dye of the formula (9). [Formula 4] [Wherein X is hydrogen, methyl or acetylamino group, Y is methoxy or ethoxy and A and B are the same or different acetoxy or oxopropoxy groups], [Formula 5] [Wherein X is hydrogen, methyl or acetylamino group, Y is hydrogen, methoxy or ethoxy and A and B are the same or different acetoxy or oxopropoxy groups], [Formula 6] [Wherein X is hydrogen, methyl or acetylamino group, Y is hydrogen, methoxy or ethoxy and A and B are the same or different hydrogen, acetoxy, methoxycarbonyl or ethoxycarbonyl group], [Formula 7] [Wherein, R ¹ and R ² are the same or different hydrogen, cyano or halogen group, A and B are the same or different hydrogen or acetoxy group; [Formula 8] [Wherein R ¹ and R ² are the same or different hydrogen or halogen groups, A and B are the same or different cyano or acetoxy groups], [Formula 9] [Wherein, R ¹ and R ² are the same or different hydrogen or halogen group, A and B are the same or different hydroxy or acetoxy groups. According to claim 1, 10 to 30% by weight of the blue azo dye of Formula 4, 10 to 20% by weight of the blue azo dye of Formula 5, 10 to 30% by weight of the blue azo dye of Formula 6, 10 to 10 of the red azo dye of Formula 7 A black dye composition containing 20% by weight, 10-30% by weight of the yellow azo dye of Formula 8, and 2-10% by weight of the brown azo dye of Formula 9. According to claim 1, 15 to 40% by weight of the blue azo dye of Formula 4, 10 to 20% by weight of the blue azo dye of Formula 5, 15 to 40% by weight of the blue azo dye of Formula 6, 5 to 5 of the red azo dye of Formula 7 Navy blue dye composition containing 10%, yellow azo dye of formula (8) 10-20%, and brown azo dye of formula (9) 0-10%. 10 to 30% by weight of the blue azo dye of Formula 4, 10 to 20% by weight of the blue azo dye of Formula 5, 10 to 30% by weight of the blue azo dye of Formula 6, red azo dye of Formula 7 as defined in claim 1 10 to 20% by weight, 10 to 30% by weight of the yellow azo dye of Formula 8, and 2 to 10% by weight of the brown azo dye of Formula 9 are formulated in the presence of naphthalenesulfonic acid / formaldehyde and lignenesulfonic acid dispersant. Method for producing a black dye composition. 15 to 40% by weight of the blue azo dye of Formula 4, 10 to 20% by weight of the blue azo dye of Formula 5, 15 to 40% by weight of the blue azo dye of Formula 6, red azo dye of Formula 7 as defined in claim 1 Navy, characterized in that 5-10%, 10-20% yellow azo dye of formula 8, and 0-10% of brown azo dye of formula 9 in the presence of naphthalenesulfonic acid / formaldehyde and lignene sulfonic acid dispersant. Method for producing a blue dye. The dyeing method of the fiber, characterized in that the dyeing of the azo dye compound as defined in claim 1 in the acetate fiber or blended fiber of these and polyester fibers.