JP3217009B2 - Disperse dye composition and method for dyeing hydrophobic fiber material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye composition and a dyeing method using the same. More specifically, the present invention relates to a water-insoluble disperse dye composition containing a specific dye and a method for dyeing hydrophobic fibers using the same.

[0002]

2. Description of the Related Art Hydrophobic fibers, especially polyester fibers, have become indispensable materials for clothing due to their excellent fiber properties. Differentiated products have also been developed by blending hydrophobic fibers with other types of fibers or by making them ultrafine fibers. In order to dye polyester fiber to black, a dyeing method using a disperse dye is generally performed.However, since a single dye cannot obtain black color, a method using a composition of a plurality of dyes or a compound dyeing method is used. The way has been done. However, in the current market, there is a deep color tone of the dyed product, and there is no defect in any of fastnesses such as light fastness, sublimation fastness, washing fastness, and water fastness. It is difficult to find a combination of. In addition, for blended products of hydrophobic fibers and recycled fibers such as rayon, cotton, and natural fibers such as wool,
The problem is that the disperse dye contaminates the regenerated fibers and natural fibers, which undesirably affects color tone and fastness. Furthermore, hydrophobic fibers composed of ultrafine fibers are called new synthetic fibers, and their excellent texture is accepted by consumers and the market is expanding, but the new synthetic fibers have a large surface area per unit weight, so light is It has the property of total reflection on the fiber surface, which greatly affects the dyeing characteristics.Dyeing the new synthetic fiber makes it more difficult to obtain a dye combination that is free from defects in both color depth and fastness. Has become.

[0003] For hydrophobic fibers, proposals regarding a disperse dye composition or a dyeing method for obtaining a deep black dyed product are disclosed in JP-B-6-192588 and JP-B-2-44.
337 and so on. However, in the dye compositions and dyeing methods described therein, even in the dyeing of ordinary polyester fibers, the color depth and light fastness, sublimation fastness, washing fastness, various fastnesses such as water fastness. In any case, it is not enough to obtain a black dyeing having no defect. Further, in the dyeing of a blended product of polyester fiber and other fibers, the stainability of the disperse dye on the regenerated fiber and the natural fiber is particularly problematic in a dark-colored dyeing such as black. In dyeing a new synthetic fiber composed of ultrafine fibers, a dye for obtaining a black dyed product having no defect in both color depth and various fastnesses is required. Thus, in black dyeing of hydrophobic fibers, development of new dyes or dyeing methods has become an important research topic.

[0004]

In the case of hydrophobic fibers, especially polyester fibers or new synthetic fibers, and blends of these with other fibers, the color tone is deep and light fastness, sublimation fastness, washing fastness, It is desired to develop a dye composition that gives a black dyed article having excellent fastnesses such as water fastness.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that hydrophobic fibers, especially polyesters, can be produced by using a dye composition containing a disperse dye having a specific structure. The present inventors have found that the above-mentioned problems can be solved by dyeing fibers, and have completed the present invention.

That is, the present invention provides the following equation (1).

[0007]

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(In the formula (1), X ₁ represents a chlorine atom or a bromine atom, and R ₁ and R ₂ each independently represent a hydrogen atom or a linear alkyl group. Here, the alkyl group has 1 carbon atom.
And four to four. A) a dye represented by formula (2):

[0009]

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(In the formula (2), X ₂ represents a chlorine atom or a bromine atom, Y represents an alkoxy group, and R ₃ and R ₄ each independently represent a hydrogen atom or a linear alkyl group. The group means a group having 1 to 4 carbon atoms.)
90% by weight and formula (3)

[0011]

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(2) A method for dyeing a hydrophobic fiber material, comprising using the disperse dye composition described in (1) above, comprising 10 to 60% by weight of the dye represented by About.

Hereinafter, the present invention will be described in detail. In dyeing hydrophobic fibers, especially polyester fibers, their blends, and ultrafine polyester fibers into black, according to the present invention, a navy blue disperse dye represented by formula (1) and formula (2) and a yellow disperse dye represented by formula (3) are used. Deep color tone, light fastness, sublimation fastness, washing fastness, water fastness, contamination of other fibers in blended products by using a dye composition containing a brown disperse dye in a specific ratio. In any of the above, it is possible to practically obtain a dyed product having no defect. The dye composition of the present invention is prepared by mixing 40 to 90% by weight of a mixture of the dyes represented by the formulas (1) and (2) and 10 to 60% by weight of the dye represented by the formula (3).
In preparing the dye composition of the present invention, a dye other than those described above may be blended, for example, for adjusting the hue, as long as the gist of the present invention is not impaired.

The dyes represented by the formulas (1), (2) and (3) used in preparing the dye composition of the present invention are all known or easily obtained by known methods. be able to. For example, the dye represented by formula (1) is described in JP-B-62-6592, the dye represented by formula (2) is described in JP-B-41-5468, and the dye represented by formula (3) is described in German Patent No. 2336717. In this way, each of the dye base powders can be easily produced.

Specific examples of the dyes represented by the formulas (1) and (2) are shown below.

Specific examples of the dye represented by the formula (1): X ₁ R ₁ R ₂ (1) -1 Cl CH ₃ CH ₃ (1) -2 Cl C ₂ H ₅ C ₂ H ₅ (1) -3 Br _{C 2 H 5 H (1)} -4 Br C 2 H 5 C 2 H 5 (1) -5 Br C 3 H 7 C 3 H 7

Specific examples of the dye represented by the formula (2): X ₁ Y R ₃ R ₄ (2) -1 Cl OC ₂ H ₅ CH ₃ CH ₃ (2) -2 Cl OC ₂ H ₅ C ₂ H ₅ C _{2 H 5 (2) -3 Br} OCH 3 C 2 H 5 H (2) -4 Br OCH 3 C 2 H 5 C 2 H 5 (2) -5 Br OCH 3 C 3 H 7 C 3 H 7

In the above specific examples, examples of more preferable dyes include (1) -4 as the compound of the formula (1), and (2) -4 as the compound of the formula (2). Can be The dye composition of the present invention has the formula (1),
After mixing the respective bulk powders of the dyes represented by the formulas (2) and (3) at the above-mentioned mixing ratio, the fine powder (dispersion) treatment may be performed to obtain a dye composition. The powders may be separately subjected to a fine-graining (dispersing) treatment and then mixed in the above-described ratio. In the latter case, a dye which has been individually made fine (dispersed) may be added to the dye bath to form the same composition as the dye composition of the present invention in the dye bath.
The mixing ratio of the dyes of the formulas (1) and (2) is usually 9: 1 to 1: 9, more preferably 7: 3 to 3: 7 by weight.

When the raw powder of the dye represented by the formula (1), the formula (2) or the formula (3) or a mixture thereof is subjected to fine particle treatment, the raw powder of the dye is generally treated with naphthalenesulfonic acid and alkylbenzene. Formalin condensate of sulfonic acid, formalin condensate of naphthalene sulfonic acid, formalin condensate of cresol sulfonic acid, cresol and 2
-Formalin condensate of naphthol-6 sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, anionic dispersant such as lignin sulfonic acid, or block copolymerization of ethylene oxide and propylene oxide In the presence of a nonionic dispersant or a mixture of these anionic dispersants and nonionic dispersants and a small amount of water, such as an ethylene oxide adduct of an alkylphenol, an ethylene oxide adduct of a polystyrene phenol, or a small amount of water. It is carried out by sufficiently wet pulverization using a pulverizer such as a sand mill. The dye composition of the present invention is subjected to dyeing in the form of a paste in the form of fine particles or after drying. In preparing the disperse dye composition of the present invention, the ratio of the dye base to the dispersant used in the preparation of the disperse dye composition is usually from 1: 9 to 1: 1, by weight of the dye base: dispersant.
1.5, preferably 1: 4 to 1: 1.

Specific examples of the hydrophobic fiber material which can be dyed by the method of the present invention include polyester fiber, triacetate fiber, diacetate fiber and blended products thereof. Blended products of natural fibers such as silk, wool and the like, ultrafine polyester fibers, cross-woven products of ultrafine polyester fibers and ordinary polyester fibers, and blended products of ultrafine polyester fibers and the above various fibers.

In order to dye a hydrophobic fiber material using the dye composition of the present invention containing the dyes represented by the formulas (1), (2) and (3) at a specific ratio, the fibers are immersed. 100 ° C. or higher, preferably 110 ° C.
It is advantageous to dye at 140 ° C. In addition, dyeing can be performed at a relatively high temperature, for example, 95 to 100 ° C. in the presence of a carrier such as O-phenylphenol or trichlorobenzene. Alternatively, the dye dispersion is padded on a cloth and
Dyeing by a so-called thermosol method of performing a dry heat treatment at 50 to 230 ° C. for 30 seconds to 1 minute is also possible. On the other hand, the dye composition of the present invention may be used with natural pastes (eg, locust bean gum, guar gum, etc.), processed pastes (eg, cellulose derivatives such as carboxymethyl cellulose, processed locust bean gum, etc.), and synthetic pastes (eg, polyvinyl alcohol, polyvinyl alcohol). Acetic acid or the like may be prepared, printed on a cloth, and then dyed by a printing method of steaming or thermosol treatment. In dyeing a hydrophobic fiber material using the dye composition of the present invention, usually 5 to 30% by weight, preferably 7 to 25% by weight based on the fiber material.
Used in proportions.

Next, the effects of the present invention will be described with reference to Tables 1 to 4. Hereinafter, “parts” and “%” are “parts by weight” and “% by weight”, respectively. Tables 1 to 4 show the results of dyeing with the dye composition of the present invention and the dye composition for comparison, respectively. As is clear from Tables 1 to 4, the dye composition of the present invention has a deeper color tone (color tone and dye exhaustion rate) in high-temperature dyeing of polyester fiber than the comparative dye composition, and the same bath of polyester fiber and cotton cloth. It is excellent in the stainability of cotton wool in dyeing, the depth of color tone (color tone and dye exhaustion rate) in the same carrier dyeing of polyester fiber and wool fabric, and the stainability of wool fabric.

[0023]

Table 1 Table 1 Depth of color tone in polyester fiber (3 denier) dyeing (Note 1) Dye composition Color tone Dye exhaustion (Note 2) Dye composition of Example 1 Deep black black 98% Comparative dye Composition (1) (Note 3) Slightly brownish black 89%

(Note 1) A pH of 4.5 was added to 8 parts of each dye composition.
Is adjusted to 3,000 parts by adding water, and 100 parts of a polyester fiber fabric (using 3 denier yarn, manufactured by Toyobo Co., Ltd.) is immersed and dyed at 130 ° C. for 60 minutes. Was added to 6 parts of 45% caustic soda, 6 parts of hydrosulfite, and 3 parts of Sunmol RC-700 (manufactured by Nika Chemical Co., Ltd., anionic surfactant) at 80 ° C. in a bath having a total amount of 3000 parts by adding water. It was subjected to reduction washing for 10 minutes, washed with water, dried, and heat-set at 180 ° C. for 30 seconds to obtain a dyed product. (Note 2) 200 mg of the stained substance was added to dimethylformamide 25.
The solution was treated at 120 ° C. for 10 minutes to extract the dye, and 2 ml of the extract was subjected to dimethylformamide / distilled water (50
/ 50) and diluted with a spectrophotometer (manufactured by Hitachi, Ltd.) to measure the absorbance at 400 nm to 700 nm. Separately, the dye composition 150 used for dyeing the dyed product was used.
was dissolved in 250 ml of distilled water, and 2 ml of the aqueous solution was dissolved in 25 ml of dimethylformamide / distilled water (50/50).
After dilution, the absorbance was measured in the same manner. These 400 nm
The exhaustion rate of the dye composition was determined from the area ratio of the absorbance spectrum at ~ 700 nm. (Note 3) 21 parts of an original dye powder represented by the following formula (4) synthesized by a method according to Japanese Patent Publication No. 40-25431, German Patent 2
9 parts of the bulk powder of the dye represented by the formula (3) synthesized by the method according to No. 336717 was added to 70 parts of Demol N (an anionic dispersant manufactured by Kao Corporation) and a small amount of water, and finely divided using a sand grinder. The resulting mixture was dispersed (dispersed) and dried to obtain a comparative dye composition (1).

[0025]

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[0026]

Table 2 Depth of color tone in polyester fiber (0.3 denier) dyeing (Note 4) Dye composition Color tone Dye exhaustion Dye composition of Example 1 Deep black 98% Comparative dye composition ( 1) Brownish black 75%

(Note 4) 24 parts of each dye composition was added with pH 4.
5 was prepared by adding water adjusted to 5 to prepare 3000 parts of dyeing bath, and 100 parts of extra fine polyester fiber woven fabric (0.3 denier, manufactured by Toyobo Co., Ltd.) was immersed and dyed at 130 ° C. for 60 minutes. The dyed product was prepared by adding water to 6 parts of 45% caustic soda, 6 parts of hydrosulfite, and 3 parts of Sunmol RC-700 (manufactured by Nika Chemical Co., Ltd., anionic surfactant) to make a total amount of 3000 parts in a bath. The resultant was subjected to reduction washing at 10 ° C. for 10 minutes, washed with water, dried, and heat-set at 180 ° C. for 30 seconds to obtain a dyed product.

[0028]

Table 3 Contamination to cotton (Note 5) Dye composition Color tone Dye exhaustion Stain (Note 6) Dye composition of Example 1 Deep black 98% 2-3 Dye composition for comparison (1) Slightly brown black 89% 1

(Note 5) A pH of 4.5 was added to 8 parts of each dye composition.
The dyeing bath was adjusted to 3,000 parts by adding water adjusted to the above, and after adding 60 parts of anhydrous sodium sulfate, 65 parts of polyester fiber woven fabric (3-denier yarn) and 35 parts of cotton gold width were immersed,
Stained at 130 ° C. for 60 minutes. 6 parts of 45% caustic soda, hydrosulfite 6
And 3 parts of Sunmole RC-700 (manufactured by Nikka Chemical Co., Ltd., anionic surfactant) were subjected to reduction washing at 80 ° C. for 10 minutes in a bath having a total amount of 3000 parts by adding water. Washing and drying were performed together with the cotton bandage to obtain a dyed product and a stained cloth.

(Note 6) The stain degree of the stained cloth was judged by the JIS stain gray scale.

[0031]

Table 4 Color depth in carrier dyeing and stainability to wool (Note 7) Dye composition Color tone Dye exhaustion rate Stainability Dye composition of Example 1 Deep black 90% 2 Comparative dye composition Product (1) Very brownish color tone 50% 1 Comparative dye composition (2) (Note 8) Brownish black 75% 1

(Note 7) A pH of 4.5 was added to 8 parts of each dye composition.
Is adjusted to 3,000 parts by adding pure water, and 5 parts of tetrocin TW (methyl naphthalene carrier, manufactured by Yamakawa Yakuhin) is added, and then 50 parts of polyester fiber fabric (3 denier) and wool are added. 50 parts of the woven fabric are dipped and 110
Stained at 60 ° C for 60 minutes. 45 dyed polyester fibers
% Of caustic soda, 6 parts of hydrosulfite, and 3 parts of Sunmol RC-700 (anionic surfactant of Kao Corporation) in a bath having a total volume of 3000 parts by adding water.
The resultant was subjected to reduction washing at 10 ° C. for 10 minutes, washed with water together with the separated wool fabric, and dried to obtain a dyed material and a stained cloth.

(Note 8) 11 parts of the original powder of the dye represented by the following formula (5) synthesized by the method of JP-B-62-6592 and the following formula (6) synthesized by the method of JP-B-41-5468
Are added to 70 parts of Demol N (manufactured by Kao Corporation, an anionic dispersant) and a small amount of water, and 10 parts of the dye bulk powder represented by the formula (3) and a small amount of water are added thereto using a sand grinder. The composition obtained by micronizing (dispersing) and drying was used as a comparative dye composition (2).

[0034]

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[0035]

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As is clear from the following Tables 5 and 6, the dye composition of the present invention is a polyester fiber (3 denier).
Good) in light fastness, sublimation fastness (stain degree and stain color of attached white cloth), water fastness, and washing fastness in ultra-fine polyester fiber (0.3 denier). It is a standard. On the other hand, the comparative dye compositions (1) to (4) have a defect in any of the fastness items. That is, a defect is observed in any of the lightfastness of class 4 or less, the other fastness of class 3 or less, and the staining color abnormality of sublimation fastness.

[0037]

Table 5 Results of fastness test on polyester fiber (3 denier) Lightfastness (Note 9) Sublimation (Note 10) Water (Note 11) Washing (Note 12) Ac contamination Ny contamination Dye composition Dye composition of Example 1 Compound 6 3-4 4 4 3-4 Comparative dye composition (1) 6-7 3-4Y 3 3-4 3-4 Comparative dye composition (2) 5-6 3-4 4 4 3-4 Comparative dye composition (3) 6 3Y4 4 3-4 (Note 13) Comparative dye composition (4) 5 3-4B 4 3-4 3-4 (Note 14)

[0038]

Table 6 Results of Fastness Test on Polyester Fiber (0.3 Denier) Lightfast Sublimation Water Laundry Dye Composition Ac Contamination Ny Contamination Dye Composition of Example 1 4-5 3 3-4 3 3 Comparative Dye Composition Product (1) 5 3Y 2 2-3 3 Comparative dye composition (2) 3-4 3 3-4 33 Comparative dye composition (3) 4-5 2-3Y 3-4 33 Comparative dye Composition (4) 3 3B 3-4 2-3 3

(Note 9) According to JIS 0842-1988, a method for testing color fastness to carbon arc lamp light. JIS
It was determined by blue scale.

(Note 10) According to JIS 0879-1975, a method for testing color fastness to dry heat treatment. Contamination of the white cloth attached to the polyester was determined by JIS gray scale.

(Note 11) JIS 0879-1975 According to the dyeing fastness test method for water. Contamination of white cloth attached to silk
Judged by IS gray scale.

(Note 12) AATCC Test Method 61 II
According to the washing color fastness test according to A. Acetate (Ac) contamination and nylon (Ny) of multifiber attached cloth
Contamination was determined by JIS gray scale.

(Note 13) 11 parts of the raw powder of the dye represented by the formula (5) synthesized by the method described in JP-B-62-6592;
10 parts of an original dye powder represented by the following formula (7) synthesized by a method according to JP-B-41-5468 and C.I. I. Disp
9 parts of original Orange 37
(Kao Corporation, anionic dispersant) 70 parts and a small amount of water are added, and finely divided (dispersed) using a sand grinder.
The resulting dye composition was dried and used as a comparative dye composition (3).

[0044]

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(Note 14) 11 parts of the raw powder of the dye represented by the formula (5) synthesized by the method according to JP-B-62-6592;
10 parts of the raw dye powder represented by the formula (7) synthesized by a known method according to JP-B-41-5468 and C.I. I. Dis
9 parts of bulk powder of Perse Orange 73 were added to 70 parts of Demol N (an anionic dispersant manufactured by Kao Corporation) and a small amount of water, finely divided (dispersed) using a sand grinder, and dried to obtain. The dye composition was designated as Comparative Dye Composition (4).

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" are "parts by weight" and "% by weight", respectively.

Example 1 11 parts of the raw powder of the dye represented by the formula (5) synthesized by the method according to JP-B-62-6592 and JP-B-41-546.
8 parts of the dye bulk powder represented by the formula (7) synthesized by the method according to No. 8 and 9 parts of the dye bulk powder represented by the formula (3) synthesized by the method according to German Patent No. 2336717 were combined with Demol N (Kao Corporation). , Anionic dispersant) and a small amount of water, and finely divided (dispersed) using a sand grinder, followed by drying to obtain a dye composition of the present invention. 8 parts (in the case of 3 denier yarn) or 24 parts (0.
Pure water adjusted to pH 4.5 was added to 3 parts of a denier yarn to prepare a dyeing bath of 3000 parts, and a polyester fiber woven fabric (using 3 denier yarn, manufactured by Toyobo Co., Ltd.) or an ultrafine polyester fiber woven fabric (0 100 parts of 0.3 denier yarn, manufactured by Toyobo Co., Ltd.), and dyed at 130 ° C. for 60 minutes. Then, the dyed product is 6 parts of 45% sodium hydroxide, 6 parts of hydrosulfite, and Sunmole RC-700 (Nichika Chemical Co., Ltd.). (An anionic surfactant) 3 parts by adding water to make the total amount 3
The resultant was subjected to reduction washing at 80 ° C. for 10 minutes in a bath of 000 parts, washed with water and dried to obtain a high-concentration deep black dyed product. Lightfastness, sublimation, water, washing, etc. of the dyed goods are 3
The fabric using denier yarn and the fabric using 0.3 denier yarn were also good.

Example 2 8 parts of the dye composition of the present invention obtained in Example 1
A dye bath adjusted to 4.5 parts by adding pure water adjusted to 4.5 was prepared, and after adding 60 parts of anhydrous sodium sulfate, 65 parts of a polyester fiber woven fabric (3-denier yarn) and 35 parts of a cotton gold width were immersed. At 130 ° C. for 60 minutes. The polyester fiber dyed product was subjected to the same reduction washing as in Example 1, washed with the separated cotton band with water and dried to obtain a high-concentration black dyed product and a stained cloth. The degree of contamination of the stained cloth was small.

Example 3 To 8 parts of the dye composition of the present invention obtained in Example 1 was added a pH
A pure water adjusted to 4.5 was added to prepare a dyeing bath of 3000 parts, and 5 parts of tetrocin TW (methylnaphthalene carrier, manufactured by Yamakawa Yakuhin) was added, and then a polyester fiber woven fabric (using 3 denier yarn) was used. (Manufactured by Toyobo Co., Ltd.) and 50 parts of wool fabric were dyed and dyed at 110 ° C. for 60 minutes. The polyester fiber dyed product was subjected to the same reduction cleaning as in Example 1, washed with water together with the separated wool fabric, and dried to obtain a high-concentration black dyed product and a stained cloth. The degree of contamination of the stained cloth was small.

Example 4 14 parts of the raw dye powder represented by the formula (5) and the formula (7)
6 parts of the dye bulk powder represented by the formula (1) and 10 parts of the dye bulk powder represented by the formula (3) are mixed with 70 parts of Demol N (an anionic dispersant manufactured by Kao Corporation) and a small amount of water, and the mixture is subjected to sand-grinding. The dye composition was formed into fine particles (dispersed) and dried under vacuum to obtain a dye composition of the present invention. 60 parts of a 20% aqueous solution of carboxymethylcellulose and 0.2 parts of tartaric acid were added to 8 parts of the dye composition, and water was added. A total of 100 parts of a printing paste was prepared and printed on a polyester georgette fabric. After drying the printing cloth, 175
Treated with superheated steam at 7 ° C for 7 minutes. A high density black print was obtained. The lightfastness, sublimation, water, washing and other fastnesses of the printed matter were all good.

[0051]

According to the dyeing method using the dye composition of the present invention, not only ordinary polyester fabrics, but also ultra-fine polyester fabrics and blended products have good fastness, high density without defects and high depth. A certain black dyed product can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/22 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (2)

(57) [Claims] (1) Formula (1) (In the formula (1), X ₁ represents a chlorine atom or a bromine atom;
R ₁ and R ₂ each independently represent a hydrogen atom or a linear alkyl group. Here, the alkyl group means one having 1 to 4 carbon atoms. And a dye represented by the formula (2): (In the formula (2), X ₂ represents a chlorine atom or a bromine atom;
Y represents an alkoxy group, and R ₃ and R ₄ each independently represent a hydrogen atom or a linear alkyl group. Here, the alkyl group means one having 1 to 4 carbon atoms. 40) to 90% by weight of a mixture of dyes represented by the formula (3): A disperse dye composition comprising 10 to 60% by weight of a dye represented by the formula: 2. A method for dyeing a hydrophobic fiber material, comprising using the disperse dye composition according to claim 1.