KR102132556B1 - Black disperse dye composition having high color fastness to washing without the effects of metamerism - Google Patents

Abstract

The present invention provides a black disperse dye composition which comprises a blue disperse dye represented by chemical formula 1 or chemical formula 2, a yellow disperse dye, and a red disperse dye, and which has high fastness to washing without metamerism.

Description

Black disperse dye composition having high color fastness to washing without the effects of metamerism}

The present invention relates to a black dispersion dye composition for dyeing fabrics such as polyester, and more particularly, to a black dispersion dye composition having no metamerism phenomenon and having excellent wash fastness (high washing). .

The dye industry is only a part of the textile industry in terms of sales, but it plays a decisive role in improving the added value of the textile industry by enabling aesthetic expression of various colors, colors, and textures of various textile materials and clothing.

As the demand for sportswear and leisure wear has increased rapidly, consumption of polyester fabrics and polyester/spandex blended fabrics is increasing. Since the product for this purpose is easy to get dirty and needs to be washed frequently, the improvement of the color fastness to washing of dyestuffs has emerged as an important aspect.

When the polyester fabric is dyed and washed after disperse dye, the dye adhered to the fiber surface is removed, but when the heat treatment is performed in the post-dyeing process, a part of the dye adhered to the fiber is transferred to the fiber surface. When washing sportswear or leisure wear made of these fabrics, a dye present on the fiber surface is detached and contaminates other fibers.

DDP-based (1,4-diketo-pyrrolo(3,4-c)pyrroes) and BDF-based (2,6-dioxo-2,6-dihydrobenzo[1,2) developed to improve the fastness to washing of these dyed products -b:4,5-b]difurans) Dye is commercially available. The dye is a high-energy type, and after dyeing, it has little staining, so there is little contamination. Although there is an advantage of improving the degree, the price of the dye is more than doubled, and it is not used much due to problems such as compatibility. As an overseas dye company, Dystar, Huntsman, etc. developed dyes using phthalimide-based or Benzodifuranone-based intermediates, and are marketed as Terasil W and WW series at Huntsman, and some colors are commercialized as XF series at Dystar. As a domestic dye company, O-Young Industrial Co., Ltd. developed the S-FW series and is currently used in some items only in Korea, and Kyung-In Yang Co., Ltd. is selling EXW series dyes using Phthalimide-based intermediates.

The present inventor has developed a high-washing liquid black dispersion dye (ARTRON BLACK SHW) through steady research and is becoming competitive in the high-washing dye market.

However, this high-washing black dispersion dye has been pointed out as a problem in which metamerism occurs after dyeing the polyester and polyester/spandex composite fibers due to the blue dye as described later in the present invention.

A metamerism phenomenon is a phenomenon in which two objects appear to have the same color under some light sources, but the color of two objects is different under other light sources. As disclosed in the present invention, a blue dye used in the production of black dye is metamerism. As a result, the final product, black dye, also shows a metamerism phenomenon in which the visible color changes depending on the light source.

In order to solve this metamerism phenomenon, Korean Patent Publication No. 2000-0072392 discloses 3,5-dinitrothiophen-2-amine, 5-nitrothiazol-2-amine, 5-nitrobenzo[c]isothiazol-3-amine-based blue dispersion. Although a black dispersion dye based on a dye has been disclosed, the metamerism properties have not reached a satisfactory level in actual experiments.

Accordingly, it is urgently required to develop a blue dye having excellent wash fastness without developing a metamerism phenomenon, and to develop a black dispersion dye containing the same.

The present invention is to solve the above object, an object of the present invention is to provide a black dispersion dye composition having excellent wash fastness (high washing) without metamerism.

In order to achieve the above object, the present invention comprises a blue-based dispersion dye represented by the following formula 1 or the following formula 2, yellow-based dispersion dye and red-based dispersion dye, black having excellent wash fastness without metamerism phenomenon A disperse dye composition is provided.

[Formula 1]

[Formula 2]

The black dispersion dye composition may be used for dyeing polyester fibers or polyester/spandex blend fibers.

In the present invention, the yellow-based dispersion dye is a known C.I. DISPERSE YELLOW 114, C.I. DISPERSE YELLOW 42, C.I. DISPERSE YELLOW 49, C.I. DISPERSE YELLOW 74, C.I. DISPERSE YELLOW 79, C.I. DISPERSE YELLOW 82, C.I. DISPERSE YELLOW 91, C.I. DISPERSE YELLOW 119, C.I. DISPERSE YELLOW 184, C.I. DISPERSE YELLOW 199, C.I. DISPERSE YELLOW 231, C.I. DISPERSE ORANGE 31, C.I. DISPERSE ORANGE 73, C.I. DISPERSE ORANGE 118 may be selected from the group consisting of, preferably C.I. DISPERSE YELLOW 114 can be used.

The red-based dispersion dye is a known DISPERSE RED HW, C.I. DISPERSE RED 167, C.I. DISPERSE RED 19, C.I. DISPERSE RED 17, C.I. DISPERSE RED 343, C.I. DISPERSE RED 1, C.I. DISPERSE RED 356, C.I. DISPERSE RED 91, C.I. DISPERSE RED 277, C.I. DISPERSE RED 311, C.I. It may be selected from the group consisting of DISPERSE RED 86, of which DISPERSE RED HW may be used.

The content of the black dispersion dye composition is preferably 10 to 40% by weight of the red-based dispersion dye, 10 to 40% by weight of the yellow-based dispersion dye, and 20 to 80% by weight of the blue-based dispersion dye.

The black dispersion dye composition according to the present invention not only has excellent wash fastness (4-5 grade), sublimation fastness (4-5 grade), but also has a very low color angle (h) and metamerism index (MI) depending on the light source. Since the phenomenon of metamerism does not occur, it can be usefully used as a fabric dye composition.

1 is a photograph showing a metamerism phenomenon in which the color of a dyed fabric looks different according to a light source (daylight, fluorescence, incandescent light).
2 is (a) LC-MASS, (b) NMR, (c) TLC data for confirming the structure of BLUE DYE 22 according to the present invention.
3 is (a) LC-MASS, (b) NMR, (c) TLC data for confirming the structure of BLUE DYE 24 according to the present invention.
FIG. 4 is a photograph showing a polyester fabric dyed with BLUE DYE 22 according to the present invention (2%, 4%) and its wash fastness and sublimation fastness.
FIG. 5 is a photograph showing a polyester fabric dyed with BLUE DYE 24 (2%, 4%) according to the present invention and its wash fastness and sublimation fastness.
Figure 6 is a photograph showing the color yield by concentration of BLUE DYE 22, BLUE DYE 24 according to the present invention.
7 is data showing a dyeing curve for each temperature according to the dyeing time of BLUE DYE 22 and BLUE DYE 24 according to the present invention.
8A to 8D are test reports of an accredited institution of polyester fabric dyed with black dispersion dye (BLACK 1) of Example 2, FIG. 8A is test reports showing wash fastness and sublimation fastness (KOTITI), and FIG. 8B is color. Each (h) (Korea Institute of Industrial Technology), Figure 8c is the Metamerism Index (MI value), Figure 8d is a test report showing the L* value (Korea Institute of Industrial Technology).
9A to 9D are test reports of an accredited organization of polyester fabric dyed with black dispersion dye (BLACK 2) of Example 3, FIG. 9A is a test report showing wash fastness and sublimation fastness (KOTITI), and FIG. 9B is color Each (h) (Korea Institute of Industrial Technology), Figure 9c is the Metamerism Index (MI value), Figure 9d is a test report showing the L* value (Korea Institute of Industrial Technology).

The black dispersion dye composition according to the present invention includes a blue-based dispersion dye represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

The black dispersion dye according to the present invention may include a yellow-based dispersion dye and a red-based dispersion dye, and the yellow-based dispersion dye is not limited, but is known C.I. DISPERSE YELLOW 114, C.I. DISPERSE YELLOW 42, C.I. DISPERSE YELLOW 49, C.I. DISPERSE YELLOW 74, C.I. DISPERSE YELLOW 79, C.I. DISPERSE YELLOW 82, C.I. DISPERSE YELLOW 91, C.I. DISPERSE YELLOW 119, C.I. DISPERSE YELLOW 184, C.I. DISPERSE YELLOW 199, C.I. DISPERSE YELLOW 231, C.I. DISPERSE ORANGE 31, C.I. DISPERSE ORANGE 73, C.I. DISPERSE ORANGE 118 can be used,

The red-based dispersion dye is not limited, but known DISPERSE RED HW, C.I. DISPERSE RED 167, C.I. DISPERSE RED 19, C.I. DISPERSE RED 17, C.I. DISPERSE RED 343, C.I. DISPERSE RED 1, C.I. DISPERSE RED 356, C.I. DISPERSE RED 91, C.I. DISPERSE RED 277, C.I. DISPERSE RED 311, C.I. DISPERSE RED 86 can be used.

The content of the black dispersion dye composition is not limited, but the blue-based dispersion dye is 20 to 80% by weight, the yellow-based dispersion dye is 10 to 40% by weight, and the red-based dispersion dye is preferably 10 to 40% by weight.

The blue-based dispersion dye according to the present invention may be two or more components including the blue-based dispersion dye represented by Chemical Formula 1 and the blue-based dispersion dye represented by Chemical Formula 2.

The ratio of the blue-based dispersion dye represented by Chemical Formula 1 and the blue-based dispersion dye represented by Chemical Formula 2 is not limited, but may be combined in a weight ratio of 2:8 to 8:2.

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

The present inventor conducted a series of studies for the development of black dispersion dyes that do not have metamerism, but have excellent physical properties such as wash fastness and sublimation fastness, and it is confirmed that these causes are mainly due to the metamerism of the blue dispersion dye. The present invention was completed by developing a black dispersion dye composition using the same through the development of a blue dispersion dye without metamerism.

The present inventor developed a high-washing black dispersion dye having excellent wash fastness by mixing the following CI Disperse Yellow 114, Disperse Red HW (high washing), and Disperse Blue HW (high washing), but metamerism phenomenon occurs depending on the light source. Was confirmed.

The color angle (hue angle) of each light source was measured for each component, and the results are shown in Table 1 below.

Light source Color angle Light source YELLOW RED BLUE BLACK D65 (daylight: daylight) 96.18 359.47 279.14 258.87 A (incandescent lamp) 88.76 369.35 15.35 315.27 CWF (fluorescent lamp) 96.74 359.88 281.21 260.90

As shown in Table 1 above, it was confirmed that the color angle difference of each light source of the black dispersion dye component is greater than that of other light sources in the A (incandescent light) light source of the metamerism color angle of the blue dye rather than the yellow and red dyes. Became.

As a result of measuring the absorption spectrum for each component, the maximum absorption wavelength range of DISPERSE YELLOW 114 is 400 to 450 nm, DISPERSE RED HW (high washing RED) is 480 to 520 nm, and DISPERSE BLUE HW (high washing BLUE) is 540 to 570 It was found to absorb the visible light region of 400 ~ 570 nm in nm. However, the actual visible light has an absorption wavelength range of 400 to 700nm. Accordingly, the present inventor conducted a study by determining that the metamerism phenomenon would be solved by using a blue dye showing an absorption spectrum of 600 nm to 700 nm in the entire range of visible light.

In order to design a blue dye showing an absorption spectrum in a long wavelength region, the present inventors selected a diazo body of a heterocyclic structure and a phthalimide structure as shown in Table 2 below as a candidate group.

On the other hand, in order to improve the wash fastness of the dye, a method is required to prevent contamination of adjacent fibers even if the dye is dissolved and dispersed in a washing bath. As a method of reducing the contamination of the adjacent fibers in the washing bath, a method of increasing the hydrophilicity of the dye or decomposing the dye that has been eliminated by the washing bath to prevent further color may be considered. Accordingly, the present inventors determined that by introducing acethoxyethyl or acethoxymethyl groups to the coupler ends, as shown in Table 2, to increase the hydrophilicity of the dye, it is possible to prevent the dye detached from the fibers from being contaminated with other fibers after washing.

Diazoze Coupler

3,5-dinitrothiophen-2-amine

5-nitrobenzo[c]isothiazol-3-amine

5-nitrothiazol-2-amine

Phthalimide계

3,5-dinitrothiophen-2-amine

5-nitrobenzo[c]isothiazol-3-amine

5-nitrothiazol-2-amine

Phthalimide series

The diazo body shown in Table 2 was a conventional reagent grade, Phthalimide-based diazo body was directly synthesized the following process.

The synthesis of the coupler shown in Table 2 was performed by the following method.

① Synthesis of Coupler 1

② Synthesis of Coupler 2

③ Synthesis of Coupler 3

④ Synthesis of Coupler 4

⑤ Synthesis of Coupler 5

⑥ Synthesis of Coupler 6

⑦ Synthesis of Coupler 7

Example 1: Synthesis of blue-based dispersion dyes

28 types of blue dyes shown in Table 3 below were prepared by reacting 4 types of diazo bodies and 7 types of couplers shown in Table 2 above.

Synthetic dyes Molecular structure BLUE DYE 1

BLUE DYE 2

BLUE DYE 3

BLUE DYE 4

BLUE DYE 5

BLUE DYE 6

BLUE DYE 7

BLUE DYE 8

BLUE DYE 9

BLUE DYE 10

BLUE DYE 11

BLUE DYE 12

BLUE DYE 13

BLUE DYE 14

BLUE DYE 15

BLUE DYE 16

BLUE DYE 17

BLUE DYE 18

BLUE DYE 19

BLUE DYE 20

BLUE DYE 21

BLUE DYE 22

BLUE DYE 23

BLUE DYE 24

BLUE DYE 25

BLUE DYE 26

BLUE DYE 27

BLUE DYE 28

The method of dye synthesis is as follows.

(1) 3,5- dinitrothiophen -2-amine In diazo Synthesis of used dye

3,5-dinitrothiophen-2-amine was diazotized with sulfuric acid and NaNO ₂ and reacted with each coupler to obtain a blue-based dispersion dye compound.

(2) 5- nitrothiazol -2-amine In diazo Synthesis of used dye

5-nitrothiazol-2-amine was diazotized with sulfuric acid and NaNO ₂ and reacted with each coupler to obtain a blue-based dispersion dye compound.

(3) 5- nitrobenzo[c]isothiazol -3-amine In diazo Synthesis of used dye

5-nitrobenzo[c]isothiazol-3-amine was diazotized with sulfuric acid and NaNO ₂ and reacted with each coupler to obtain a blue-based dispersion dye compound.

(4) Phthalimide series In diazo Synthesis of used dye

5-amino-4,6-dibromo-2-butyl phthalimide was diazotized with sulfuric acid and NaNO ₂ and reacted with each coupler to prepare a bromination dye. After dissolving in DMSO, NaCN and CuCN were only half of the input. After adding and stirring at room temperature for 1 hour, the other half was added, heated to 50°C, stirred for 5 minutes, and then water was added, followed by stirring for 30 minutes, followed by filtration washing with water to obtain a blue-based dispersion dye compound.

28 kinds of dyes synthesized by the above method were mixed with distilled water together with a dispersant (dywell 500: a naphthalene sulfonic acid condensate) to prepare a dispersion dye salt solution having a particle size of 0.7 µm or less using glass beads for dyeing. .

① Equipment used: Basket Mill (NC Tech)

② Dye used: Blue dye 1 to 28 synthesized

③ Dispersant: Naphthalene sulfonic acid condensate

The mixing ratio is shown in Table 4 below.

Synthesized BLUE P/C Dispersant water BEADS input % 10% 5.6% 14% 70%

Experimental Example 1: Properties test of synthetic blue dispersion dye

Synthesis yield of the blue-based dyes prepared in Example 1, maximum absorption wavelength, wash fastness and sublimation fastness of the polyester dyed fabric, and color angle (h) were tested and are shown in Table 7 below. Accordingly, a blue-based dispersion dye suitable for the present invention was selected and tested by the method of Table 6 below.

Composite yield Absorption wavelength Washing fastness Sublimation fastness Color angle (h) 60% or more 595nm or more Level 4 or higher Level 4 or higher 8 or less

Key performance indicators Sample definition How to measure Difference in color angle (h) Difference in color angle of incandescent light source based on D65 light source CCM
(Computer color matching) Washing fastness Tested with standardized measurement methods to rank the degree of contamination Tested by KS K ISO 105 C06(A2S) method Sublimation fastness Tested with standardized measurement methods to rank the degree of contamination Test by KS K 0651 method

Dye name Composite yield
(%) UV λmax
(nm) Laundry Color fastness
(class) sublimation Color fastness
(class) Color angle
(h) Applicable
Whether BLUE DYE 1 22.9% 650.5nm 3 2-3 5.8 Not applicable BLUE DYE 2 32.4% 592.0nm 3-4 4-5 6.2 Not applicable BLUE DYE 3 76.5% 668.5nm 2-3 4 7.3 Not applicable BLUE DYE 4 24.4% 647.5nm 3 3-4 0.5 Not applicable BLUE DYE 5 87.8% 624.0nm 3 2-3 1.3 Not applicable BLUE DYE 6 69.5% 652.5nm 3-4 4 5.4 Not applicable BLUE DYE 7 54.3% 594.5nm 3-4 3-4 4.2 Not applicable BLUE DYE 8 87.5% 603.0nm 3-4 4 2.3 Not applicable BLUE DYE 9 66.7% 575.5nm 3 3-4 1.5 Not applicable BLUE DYE 10 76.9% 619.5nm 3 4 1.3 Not applicable BLUE DYE 11 31.2% 627.5nm 3-4 4 2.5 Not applicable BLUE DYE 12 71.2% 606.0nm 2-3 3 2.8 Not applicable BLUE DYE 13 96.4% 607.0nm 3 4 1.7 Not applicable BLUE DYE 14 80.1% 577.0nm 3 3 3.5 Not applicable BLUE DYE 15 47.6% 598.5nm 4 4 0.4 Not applicable BLUE DYE 16 15.5% 549.5nm 4 3 2.3 Not applicable BLUE DYE 17 10.8% 612.5nm 3-4 4 4.6 Not applicable BLUE DYE 18 13.7% 614.0nm 3-4 3 6.5 Not applicable BLUE DYE 19 23.7% 580.0nm 4-5 2 5.8 Not applicable BLUE DYE 20 12.2% 592.0nm 3-4 3 3.2 Not applicable BLUE DYE 21 23.0% 544.0nm 4 4-5 2.9 Not applicable BLUE DYE 22 66.9% 599.0nm 4 4-5 5.8 Applicable BLUE DYE 23 88.1% 549.0nm 4 4 4.5 Not applicable BLUE DYE 24 65.8% 616.5nm 4-5 4-5 1.7 Applicable BLUE DYE 25 22.5% 610.0nm 4 4 8.4 Not applicable BLUE DYE 26 82.7% 586.5nm 3-4 3-4 7.6 Not applicable BLUE DYE 27 45.9% 600.5nm 4-5 4 9.7 Not applicable BLUE DYE 28 76.5% 550.0nm 4 4 4.9 Not applicable

As shown in Table 7, the result of physical properties test of 28 newly synthesized dyes was 60% or more, the maximum absorbance was 595nm or more, and the results of screening and washing sublimation fastness were selected as dyes having a level of 4 or higher. The dyes using the Phthalimide pigment matrix of BLUE DYE 22 and BLUE DYE 24 showed good results.

2 is (a) LC-MASS, (b) NMR, (c) TLC data for confirming the structure of the BLUE DYE 22 according to the present invention, and FIG. 3 is for confirming the structure of the BLUE DYE 24 according to the present invention ( a) LC-MASS, (b) NMR, (c) TLC data.

FIG. 4 is a photograph showing a polyester fabric dyed (2%, 4%) with BLUE DYE 22 according to the present invention and its wash fastness and sublimation fastness, and FIG. 5 is dyed with BLUE DYE 24 according to the present invention (2% , 4%) This is a photograph showing a polyester fabric and its wash fastness and sublimation fastness.

Experimental Example 2: BUILD UP characteristic test of synthetic blue dispersion dye

The results of confirming the color yield (concentration 2%, 4%, 6%, 8%) of each concentration of DIPSERSE BLUE HW as a control with BLUE DYE 22 and BLUE DYE 24 synthesized in Example 1 are shown in FIG. 6.

As shown in Figure 6, both BLUE DYE 22 and BLUE DYE 24 showed high color yield in high-density dyeing, and in particular, in the case of BLUE DEY 24, it can be seen that it shows superior color yield compared to the existing high-washing BLUE dye (DISPERSE BLUE HW). .

Experimental Example 3: By temperature according to dyeing time Dyeing curve exam

Yellow dyes, red dyes and black dyes used in high-wash black dye products for blending to produce black dyes. Star dyeing curve test was conducted and the results are shown in FIG. 7.

As shown in FIG. 7, as a result, both BLUE DYE 22 and BLUE DYE 24 show more dyeing properties similar to yellow dyes and red dyes than conventional high-washing blue dyes (DISPERSE BLUE HW), indicating that the dyeing properties are excellent.

Example 2: Preparation of a black dispersion dye composition (BLACK 1) comprising BLUE DYE 22, BLUE DYE 24

Two components of BLUE DYE 24 (Formula 1) and BLUE DYE 22 (Formula 2) synthesized in Example 1 with a blue dye, and commercially available C.I. A black dispersion dye was prepared by mixing DISPERSE YELLOW 114 (Formula 3) and DISPERSE RED HW (Formula 4) developed by the applicant.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

When preparing the black dispersion dye, BLUE DYE 24, BLUE DYE 22, YELLOW, and BLUE dyes were formulated at a weight ratio of 36%:34%:15%:15%.

Example 3: Preparation of a black dispersion dye composition (BLACK 2) containing BLUE DYE 24

BLUE DYE 24 (Formula 1) synthesized in Example 1, and commercially available C.I. A black dispersion dye was prepared by mixing DISPERSE YELLOW 114 (Formula 3) and DISPERSE RED HW (Formula 4) developed by the applicant.

When preparing the black dispersion dye, BLUE DYE 24, YELLOW, and BLUE dyes were formulated at a weight ratio of 70%:15%:15%.

Experimental Example 4: Properties of BLACK 1 dispersion dye and BLACK 2 dispersion dye

The polyester fabric dyed with the black dispersion dye (BLACK 1) of Example 2 and the black dispersion dye (BLACK 2) of Example 3 was commissioned by the Korea Institute of Industrial Technology and KOTITI Testing Institute, an accredited testing organization, according to Table 8. Performance verification was performed and the results are shown in FIGS. 8A to 9D, and are summarized in Table 9 below.

8A to 8D are test reports of an accredited institution of polyester fabric dyed with black dispersion dye (BLACK 1) of Example 2, FIG. 8A is test reports showing wash fastness and sublimation fastness (KOTITI), and FIG. 8B is color. Each (h) (Korea Institute of Industrial Technology), Figure 8c is a Metamerism Index (MI value), Figure 8d is a test report showing the L* value (Korea Institute of Industrial Technology).

9A to 9D are test reports of an accredited organization of polyester fabric dyed with black dispersion dye (BLACK 2) of Example 3, FIG. 9A is a test report showing wash fastness and sublimation fastness (KOTITI), and FIG. 9B is color Each (h) (Korea Institute of Industrial Technology), Figure 9c is the Metamerism Index (MI value), Figure 9d is a test report showing the L* value (Korea Institute of Industrial Technology).

Key performance indicators Sample definition How to measure Difference in color angle (h) Difference in color angle of incandescent light source based on D65 light source CCM
(Computer color matching) Metamerism index
(MI) Measure MI value at incandescent light source with reference specimen based on D65 light source CCM
(Computer color matching) Lightness (L*) The L value is a lightness value, and the smaller the value, the darker the color. CCM
(Computer color matching) Washing fastness Tested with standardized measurement methods to rank the degree of contamination Tested by KS K ISO 105 C06(A2S) method Sublimation fastness Tested with standardized measurement methods to rank the degree of contamination Test by KS K 0651 method

8% BLACK 1 dispersion dye (Example 2) BLACK 2 dispersion dye (Example 3) Washing fastness
(KS K ISO 105-C06) Level 4-5 Level 4-5 Sublimation fastness
(KS K 0651) Level 4-5 Level 4-5 Color angle (h)
(Incandescent light source) 6.50 2.94 Metamerism index
(MI value) 0.05 0.18 L* 14.40 14.62

As shown in Figures 8a to 9d and Table 9, black dispersion dyes according to the present invention were all excellent in color fastness (h), Metamerism Index, with wash fastness levels 4-5 and sublimation fastness levels 4-5. It can be seen that metamerism does not occur due to the excellent (MI).

Claims (5)

delete delete It includes a blue-based dispersion dye represented by the following formula (1), yellow-based dispersion dye represented by the following formula (3) and red-based dispersion dye represented by the following formula (4), excellent washing fastness without metamerism phenomenon Black dispersion dye composition having a.
[Formula 1]

[Formula 3]

[Formula 4]

A black dispersion dye composition comprising a blue-based dispersion dye represented by the following Chemical Formulas 1 and 2, a yellow-based dispersion dye represented by the following Chemical Formula 3, and a red-based dispersion dye represented by the following Chemical Formula 4.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

The method of claim 3 or 4,
The content of the black dispersion dye composition is 20 to 80% by weight of the blue-based dispersion dye, 10 to 40% by weight of the yellow-based dispersion dye, characterized in that the red-based dispersion dye 10 to 40% by weight, black dispersion dye composition .

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