JP2002332423A - Disazo compound and dyeing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a disazo compound which has a high dyeing property for cellulosic fibers and can efficiently dye the cellulosic fibers in good reproducability, and to provide a dyeing method. SOLUTION: This disazo compound represented by general formula (1) R1 is H or methoxy; R2 is H, methyl, methoxy, ureido or acetylamino; R3 is H or methoxy; R4 is H, methyl, acetylamino or ureido; (m) is 2 or 3} in the form of the free acid or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a disazo compound as a reactive dye and a method for dyeing cellulosic fibers using the same.

[0002]

2. Description of the Related Art Various reactive dyes have been conventionally known and are widely used in the field of dyeing cellulosic fibers. For example, dyes having a reactive group such as monochlorotriazinyl, monofluorotriazinyl fluorochloropyrimidinyl, dichloroquinoxazinyl, vinylsulfonyl, sulfate ethylsulfonyl and the like, which are acid binders such as sodium carbonate , Sodium hydroxide, sodium metasilicate, etc., the pH of the dye bath is 10 or more,
It is dyed at a temperature of 100 ° C. or less. At the time of this dyeing, in order to avoid uneven dyeing, reduction in color yield due to hydrolysis, and the like, usually, a method in which an acid binder is added stepwise during dyeing is often used. On the other hand, as a mixed fiber containing a cellulosic fiber, particularly, since a blended product of polyester fiber and cotton has excellent clothing properties,
Used in large quantities. The disperse dye for dyeing the polyester fiber side is usually applied in an acidic to neutral dyeing bath, generally at a temperature of 100 to 140 ° C., in order to avoid decomposition and deterioration of the dye itself. Therefore, in dyeing this blended product, in the two-bath method in which each fiber is treated with a different dyeing bath, or in the same dyeing bath, slide the application conditions of the dye to each fiber, One-bath two-stage method for dyeing is widely used.

[0003]

However, in order to shorten the dyeing time, save energy, and simplify the processing operation of the dyeing process, delicate and complicated adjustment of drug addition during dyeing is required for the above dyeing. There is a demand for an efficient one-bath one-step method of simultaneously dyeing the same dyeing bath in the same dyeing bath in the case of a rational dyeing method without the use of a polyester fiber and cotton. In this case, with respect to the reactive dye, under the dyeing conditions of the disperse dye on the polyester fiber, the dye bath has a pH of acidic to neutral, a temperature of 100 to 140 ° C., a stability not causing decomposition, and a high dyeing property. It is required to have. Several dyes have been proposed along the gist of the invention, and those related to the yellow dye field of the present invention are described in, for example,
JP-A-86168, JP-A-1-308460, etc., but do not necessarily have sufficient properties. For example, they do not show sufficient dyeing properties in a relatively low temperature region around 100 ° C. , High color yield cannot be obtained, and there is a problem of color breakage and uneven dyeing when blended with other dyes. It is highly desirable to develop reactive dyes that show good dyeing properties, have good reproducibility, are excellent in various fastnesses, light fastness, chlorine fastness, washing fastness, etc., and have no problems in thermal discoloration, phototropy, etc. It is rare.

[0004]

Under these circumstances, the present inventors have developed a reactive dye which has high dyeability in a wide range of pH from acidic to neutral and has excellent reproducibility. As a result of intensive studies for development, a disazo compound meeting the purpose was found, and the present invention was completed.

That is, the present invention relates to (1) a compound represented by the general formula (1):

[0006]

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(In the formula (1), R ₁ represents a hydrogen atom or a methoxy group, and R ₂ represents a hydrogen atom, a methyl group, a methoxy group,
R ₃ represents a hydrogen atom or a methoxy group, R ₄ represents a hydrogen atom, a methyl group,
Represents an acetylamino group or a ureido group, and m is 2 or 3
Represents And (2) a method for dyeing a cellulosic fiber, characterized by using the disazo compound described in (1).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The disazo compound of the present invention is a compound of the formula (1)
These are synthesized, for example, by the following method. Formula (2) in the form of free acid

[0009]

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(In the formula (2), m represents the same meaning as described above.) The compound represented by the general formula (3)

[0011]

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(In the formula (3), R ₁ and R ₂ have the same meanings as described above.) The compound reacts with a compound represented by the general formula (4) in the form of a free acid.

[0013]

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(In the formula (4), R ₁ , R ₂ , and m have the same meanings as described above.) This reaction is
Diazotization is a conventional method using hydrochloric acid and sodium nitrite, at a temperature of 0 to 20 ° C, and a coupling reaction at a temperature of 0 to 30 ° C.
Performed at pH 3-8. After the reaction, the reaction product is usually salted out with sodium chloride or the like, filtered and isolated. On the other hand, the general formula (5)

[0015]

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The compound represented by the general formula (6)

[0017]

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(In the formula (6), R ₃ and R ₄ have the same meanings as described above.) The compound reacts with a compound represented by the general formula (7) in the form of a free acid.

[0019]

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(In the formula (7), R ₃ and R ₄ have the same meanings as described above.) In this reaction, diazotization is carried out by a conventional method using hydrochloric acid and sodium nitrite, and the temperature is 0 to
At 20 ° C, the coupling reaction is carried out at a temperature of 0-30 ° C, pH
3 to 8 are performed. Subsequently, a cyanuric chloride is condensed with the compound of the formula (4) or the compound of the formula (7) in any order, and the compound of the formula (8)

[0021]

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(In the formula (8), R ₁ , R ₂ , R ₃ , R ₄ , and m have the same meanings as described above.) In this reaction, the first condensation is performed in water at a temperature of 0 to 30 ° C. and a pH of 2
At ~ 8, the second condensation is carried out at a temperature of 30-70 ° C, pH 3-8.
It is performed in. Next, the compound of the formula (8) is reacted with nicotinic acid to obtain a disazo compound represented by the formula (1). This reaction is carried out in water at a temperature of 80-100 ° C., p
H4 to H7.

The disazo compound of the formula (1) of the present invention may be in the form of a free acid, a salt thereof, or a mixture thereof. Preferred are alkali metal salts and alkaline earth metal salts, particularly Na salts, K salts and Li salts. Usually, if necessary, it is isolated in the form of these salts by salting out or the like.

In producing the disazo compound of the above formula (1), specific examples of the compound of the above formula (2) to be used include a free acid form, m = 2 and 2-amino-
3,6-naphthalenedisulfonic acid, 2-amino-4,8
-Naphthalenedisulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, 2-amino-6,8-naphthalenedisulfonic acid, and the like, wherein m is 3, for example, 2-amino-3,6,8-naphthalene Trisulfonic acid, 2-amino-4,6,8-naphthalenetrisulfonic acid and the like.

Specific examples of the compound of the formula (3) include, for example, aniline, 2-methoxyaniline, 3-methylaniline, 3-methoxyaniline, 3-acetylaminoaniline, 3-ureidoaniline, 5-dimethoxyaniline, 2-methoxy-5-methylaniline, 2
-Methoxy-5-acetylaminoaniline and the like.

On the other hand, specific examples of the compound of the above formula (5) include 2-aminobenzenesulfonic acid,
3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid and the like. Specific examples of the compound of the formula (6) include aniline, 2-methoxyaniline, 3-methylaniline, 3-acetylaminoaniline, 3-ureidoaniline, 2-methoxy-5-methylaniline, 2-
Methoxy-5-acetylaminoaniline and the like.

The disazo compound of the formula (1) of the present invention can also be applied to the dyeing of cellulosic fibers, for example, the dip dyeing method, the continuous dyeing method by padding by a usual method, and the printing method. The bath ratio of the dyeing method of the present invention, for example, the dip dyeing method, is usually from 1: 5 to 1:50. As the fiber material that can be dyed by the dyeing method of the present invention, cotton, hemp, rayon, polynosic, cupra, Tencel or the like alone or
These mixed fibers, further, these and other fibers, for example,
Polyester fiber, acetate fiber, polyacrylonitrile fiber, wool, silk, blended with polyamide fiber such as nylon or the like, or mixed fabric can be mentioned.

The disazo compound of the present invention contains a cellulosic fiber as a reactive dye because it has a stable and high dyeing property in a dye bath pH of 5 to 9 and a temperature range of 95 to 140 ° C. As a mixed fiber, a mixed fiber of polyester fiber and cotton is extremely useful for a rational single-bath one-step dyeing method using a combined use of a disperse dye. The one-bath one-step dyeing of a blended product of polyester fiber and cotton is performed, for example, as follows.
The disazo compound of the formula (1), a disperse dye, an inorganic salt (for example, sodium sulfate, salt and the like) as necessary, a buffer for maintaining the pH at 5 to 9, a surfactant (a dispersant, a penetrant, and the like), a reduction inhibitor To prepare a dye bath, immerse the blended product in this,
Stain at 100-140 ° C for 20-90 minutes. afterwards,
Perform soaping in the usual way. Further, since the disazo compound of the present invention exhibits high dyeing properties even in a relatively low temperature region around 100 ° C., it is usually a basic dye which is dyed at a temperature of about 100 ° C., from acidic to neutral dyeing bath. It is also useful for the application of the one-bath method to dyeing of polyacrylonitrile fiber by the use of an acid dye, blending of wool, silk, or polyamide fiber such as nylon and cellulose-based fiber with an acid dye. The disazo compound of the present invention is not limited to the above-mentioned objects, and can be similarly applied to a fibrous material containing only cellulosic fibers. When performing this staining,
It is a matter of course that the fiber material is first treated in a dye bath at a temperature of about 40 to 100 ° C., and then an ordinary method of adding an acid binder to the dye bath and dyeing can be employed. To
A so-called all-in-one dyeing method in which an acid binder or a buffer at a pH of 5 to 9 is added in advance and dyed in advance can be applied. By using the disazo compound of the present invention, it is possible to avoid inconveniences such as reduction in color yield due to hydrolysis, disproportionate dyeing, color breakage during compound dyeing, etc. due to the addition of a delicate and complicated acid binder during dyeing. In addition, dyeing can be performed with high reproducibility along with the efficiency of the process. When dyeing,
The disazo compounds of the present invention can be used alone or in combination of two or more. In addition to the disazo compound of the present invention, a reactive dye, a disperse dye, an acid dye, etc. other than the disazo compound of the present invention can be used in combination, if desired.

In the dyeing method of the present invention, usable acid binders or buffers are not particularly limited. Examples of the acid binder include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and metasilicate. Buffers such as sodium, trisodium phosphate, tripotassium phosphate, sodium pyrophosphate, potassium pyrophosphate and sodium trichloroacetate include acetic acid + sodium acetate, monosodium phosphate + disodium phosphate monopotassium phosphate + disodium phosphate, maleic acid + Borax, etc., if necessary,
These can be used alone or in appropriate combination. In the dyeing method of the present invention, when performing dyeing, if necessary, known additives, for example, a dissolution aid, a dispersant,
Emulsifier, leveling agent, slow dyeing agent, carrier agent, color development accelerator,
Precipitation inhibitors, sequestering agents, oxidation or reduction inhibitors, and the like can be used.

The disazo compound represented by the above formula (1) can be used as a reactive dye stably in the temperature range of 95 to 140 ° C. in the presence of a buffering agent which maintains the dye bath at pH 5 to 9. It has high dyeing properties and can perform high color yield, build-up properties, level dyeing properties, and excellent reproducibility on cellulosic fibers. From this property, it is extremely effective to apply a rational single-bath single-stage dyeing method as a mixed fiber containing a cellulosic fiber, particularly a mixed fiber of polyester fiber and cotton, in combination with a disperse dye. Of course, the subject is not limited to this, as a cellulosic fiber material, cotton, hemp, rayon, polynosic, cupra, Tencel alone or a mixed fiber thereof, also shows suitable properties, Excellent in various fastnesses, light resistance, chlorine resistance, washing resistance, etc., thermal discoloration,
Dyeing that does not have a problem in phototropic properties can be performed. Furthermore, not only these and polyester fibers, but also wool, silk, polyamide fibers such as nylon, acetate fibers, and blended products such as polyacrylonitrile fibers,
Dyeing can be carried out effectively using acid dyes, disperse dyes, and basic dyes as the respective dyes.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. In the examples, parts represent parts by weight.

Example 1 2-Amino-4,8-naphthalenedisulfonic acid was diazotized, subjected to a coupling reaction with 3-acetylaminoaniline, then salted out with sodium chloride, and separated by filtration. 23.2 parts of-(4-amino-2-acetylaminophenylazo) -4,8-naphthalenedisulfonic acid were dissolved in 300 parts of water by adding sodium hydroxide. 9.3 parts of cyanuric chloride was added thereto, and the mixture was added at 0 to 5 ° C and pH 5 to 5.
At 7, primary condensation was performed. During the reaction, sodium carbonate was added to complete the reaction. Then, 13.8 parts of 4- (4-aminophenylazo) benzenesulfonic acid was added to water 2
After dissolving and adding to 00 parts, secondary condensation was carried out at 50 ° C. and pH 6 to 7. Then, 12 parts of nicotinic acid was added to 10 parts of water.
The suspension was added to 0 parts, and the reaction was completed at 95 ° C. and pH 6 to 7. Thereafter, salting out is carried out, and the formula (9) is obtained in the form of a free acid.

[0033]

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Thus, 41 parts of a disazo compound represented by the following formula was obtained.
This compound was very well soluble in water, and the maximum absorption wavelength of the solution was 365 nm. The compound 4- (4-aminophenylazo) benzenesulfonic acid used in the present example was obtained by coupling reaction of aniline sulfomethylated with formalin and sodium bisulfite and 4-aminobenzenesulfonic acid diazotized in advance. And then
The sulfomethyl group was hydrolyzed under alkali, salted out and separated.

Example 2 2-Amino-3,6,8-naphthalenetrisulfonic acid was diazotized and subjected to a coupling reaction with 3-aceacetylaminoaniline, followed by salting out with sodium chloride and separation by filtration. 2- (4-Amino-2-acetylaminophenylazo) -3,6,8-naphthalenetrisulfonic acid (27.2 parts) obtained as above was added with sodium hydroxide and added to water 30.
Dissolved in 0 parts. 9.3 parts of cyanuric chloride are added here,
Primary condensation was performed at 0 to 5 ° C and pH 5 to 7. During the reaction,
The reaction was completed by adding sodium carbonate. Next, 13.8 parts of 4- (4-aminophenylazo) benzenesulfonic acid was dissolved in 200 parts of water and added thereto.
Secondary condensation was performed at H6 to H7. Next, 12 parts of nicotinic acid were suspended in 100 parts of water and added thereto.
The reaction was completed at 6 to 7 to complete the reaction. Thereafter, salting out is carried out, and the formula (10) is obtained in the form of a free acid.

[0036]

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44 parts of a disazo compound represented by the following formula were obtained.
This compound was well dissolved in water, and the maximum absorption wavelength of the solution was 377 nm.

Examples 3 to 18 Disazo compounds having the structure shown in Table 1 below were synthesized in the form of the free acid in the following general formula (11) in accordance with Example 1.
The results show the maximum absorption wavelength (nm) of the aqueous solution.

[0039]

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Table 1 Example Naphthalene ring Benzene ring SO3H group position R1 R2 SO3H group position R3 R4 Maximum absorption wavelength (nm) 3,4,8 HH 4 HH 355 4 4,8 H NHCOCH3 3 OCH3 H 366 5 4,8 H OCH3 3 OCH3 H 368 6 4,8 H NHCONH2 4 HH 373 7 4,8 H NHCONH2 4 H NHCONH2 375 8 4,8 OCH3 CH3 4 H NHCOCH3 378 9 6,8 H NHCOCH3 4 HH 369 10 6,8 H NHCOCH3 3 H CH3 370 11 6,8 H NHCONH2 4 H NHCONH2 376 12 6,8 OCH3 H 3 OCH3 H 366 13 6,8 H CH3 3 H CH3 368 14 3,6 H NHCOCH3 4 HH 367 15 3,6 H NHCONH2 3 H CH3 374 16 3,6 H CH3 4 H CH3 366 17 5,7 H NHCOCH3 4 HH 362 18 5,7 H NHCONH2 4 H NHCOCH3 370

Examples 19 to 29 Disazo compounds having the structure shown in Table 2 below were synthesized in the form of the free acid in the following general formula (12) according to Example 2.
The results show the maximum absorption wavelength (nm) of the aqueous solution.

[0042]

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Table 2 Example Naphthalene ring Benzene ring SO3H group position R1 R2 SO3H group position R3 R4 Maximum absorption wavelength (nm) 19 3,6,8 HH 4 HH 371 20 3,6,8 H NHCOCH3 3 OCH3 H 379 21 3,6,8 H OCH3 3 OCH3 H 381 22 3,6,8 H NHCONH2 4 HH 384 23 3,6,8 H NHCONH2 4 H NHCONH2 385 24 3,6,8 OCH3 CH3 4 H NHCOCH3 390 25 4,6 , 8 H NHCOCH3 4 HH 371 26 4,6,8 H NHCOCH3 3 H CH3 372 27 4,6,8 H NHCONH2 4 H NHCONH2 379 28 4,6,8 H CH3 3 H CH3 369 29 4,6,8 OCH3 H 4 H NHCOCH3 368

Example 30 0.5 part of the disazo compound obtained in Example 2 and Glauber's salt 60
Parts, 2 parts of disodium phosphate, 0.5 parts of monopotassium phosphate,
Water was added to 1 part of sodium metanitrobenzenesulfonate to prepare a dye bath having a total volume of 1000 parts. At this time, the pH value of the dye bath was 7. 50 parts of a cotton knit were fed into this dyeing bath, the temperature was raised to 130 ° C. in 30 minutes, and dyeing was carried out at the same temperature for 40 minutes. The pH value after staining was 7 as before. Next, after washing with water and soaping at 100 ° C. with an aqueous solution containing an anionic surfactant, washing with water and drying were performed to obtain a yellow dyed product. The dyed product obtained had a high color yield, was uniformly dyed, had no problems of thermal discoloration and phototropy, and had good light fastness, chlorine fastness and washing fastness.

Example 31 0.3 parts of the disazo compound obtained in Example 1, Kay
0.15 parts of acelon Yellow E-3GL (manufactured by Nippon Kayaku Co., Ltd., disperse dye),
Yellow E-BRLCONC (Nippon Kayaku Co., Ltd.)
Disperse dye) 0.05 parts, Glauber's salt 60 parts, sodium metanitrobenzenesulfonate 1 part, formalin condensate of naphthalenesulfonic acid (dispersant) 2 parts, disodium phosphate 2
To 0.5 parts of monopotassium phosphate, water was added to prepare a dye bath having a total volume of 1,000 parts at pH 7. 50 parts of a mixed fiber of polyester fiber / cotton (50/50) is fed into the dyeing bath,
The temperature was raised to 130 ° C. in 30 minutes, and dyed at the same temperature for 60 minutes. Next, after washing with water and soaping at 100 ° C. with an aqueous solution containing an anionic surfactant, washing with water and drying were performed to obtain a yellow dyed product. The obtained dyed product was uniformly dyed on both the polyester fiber side and the cotton side, had a high color yield, and had good light fastness, chlorine fastness and washing fastness.

Example 32 0.3 parts of the disazo compound obtained in Example 1, Kay
acelon Yellow E-3GL 0.15
Department, Kayacelon Yellow E-BRLCO
NC 0.05 parts, Glauber's salt 60 parts, formalin condensate of naphthalenesulfonic acid (dispersant) 2 parts, Mignol RP10
Water (3 parts, 0 (manufactured by KK, special emulsifier), 2 parts of disodium phosphate, 0.5 part of monopotassium phosphate) was added to prepare a dye bath having a total volume of 1,000 parts at pH 7. 50 parts of a mixed fiber of polyester fiber / cotton (50/50) was fed into the dyebath, heated to 100 ° C. in 30 minutes, and dyed at the same temperature for 60 minutes. Next, after washing with water and soaping at 100 ° C. with an aqueous solution containing an anionic surfactant, washing with water and drying,
A yellow dyeing was obtained. The obtained dyed product was uniformly dyed on both the polyester fiber side and the cotton side in the same manner as in Example 31, and had high color yield and good fastness.

Example 33 0.5 parts of the disazo compound obtained in Example 2 and sodium sulfate 60
, 2 parts of disodium phosphate and 0.5 part of monopotassium phosphate, water was added to prepare a dye bath having a total volume of 1000 parts. At this time, the pH value of the dye bath was 7. Cotton knit 5
0 parts, heated to 95 ° C. in 30 minutes,
Stained for 0 minutes. The pH value after staining was 7 as before. Next, after washing with water and soaping at 100 ° C. with an aqueous solution containing an anionic surfactant, washing with water and drying were performed to obtain a yellow dyed product. The resulting dyed product had a high color yield and was uniformly dyed, as in Example 30.
Each fastness was good.

Example 34 0.5 parts of the disazo compound obtained in Example 2, Kay
0.5 parts of acelon React Blue CN-MG (manufactured by Nippon Kayaku Co., Ltd., reactive dye), 60 parts of Glauber's salt, 2 parts of disodium phosphate, and 0.5 part of monopotassium phosphate are mixed with water, and a total volume of pH 7 is 1000 parts. Was prepared. 50 parts of a cotton knit were fed into this dyeing bath, the temperature was raised to 95 ° C. in 30 minutes, and dyeing was carried out at the same temperature for 60 minutes. The pH value after staining was 7 as before. Next, after washing with water and soaping at 100 ° C. with an aqueous solution containing an anionic surfactant, washing with water and drying were performed to obtain a green dyed product. At the time of dyeing, the compatibility of the compound dyeing is in good agreement, and the dyed material has a similar hue, and the obtained dyed material has no problems such as color breakage, uneven dyeing, etc., and is uniformly dyed, Excellent reproducibility.

Example 35 0.3 parts of the disazo compound obtained in Example 1, Kay
0.2 parts of anol Milling Yellow 5GW (Nippon Kayaku Co., Ltd., acid dye), Kayanol
Water was added to 0.04 part of Milling Yellow RW new (manufactured by Nippon Kayaku Co., Ltd., acid dye), 30 parts of sodium sulfate, 2 parts of disodium phosphate, and 0.5 part of monopotassium phosphate,
A total of 1000 parts of a dye bath having a pH of 7 was prepared. Into this dyeing bath, 50 parts of a nylon / cotton (50/50) mixed woven fabric were fed, heated to 100 ° C. in 30 minutes, and dyed at the same temperature for 60 minutes. Next, after washing with water and soaping at 100 ° C. with an aqueous solution containing an anionic surfactant, washing with water and drying were performed to obtain a yellow dyed product. The resulting dyed product was uniformly dyed on both the nylon side and the cotton side, and had a good color yield.

[0050]

EFFECT OF THE INVENTION By using the disazo compound of the present invention, cellulosic fibers can be produced with good leveling properties and high reproducibility, high color yield and various fastnesses, good thermochromic properties and good phototropic properties. Dyeing could be performed. Using a blend of polyester fiber and cotton in combination with a disperse dye, dyeing with excellent reproducibility was achieved by the rational one-bath one-step method and the cellulosic fiber by the efficient all-in-one method.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasuo Shirasaki 61-7 Minaminakano, Omiya-shi, Saitama F-term (reference) 4C063 AA01 BB02 CC44 DD12 EE10 4H056 JA06 JB02 JC14 4H057 AA02 BA07 BA24 DA01 DA24 EA01 GA07

Claims (2)

[Claims] 1. A compound of the general formula (1) in the form of a free acid (In the formula (1), R ₁ represents a hydrogen atom or a methoxy group,
R ₂ represents a hydrogen atom, a methyl group, a methoxy group, an acetylamino group or a ureido group, R ₃ represents a hydrogen atom or a methoxy group, and R ₄ represents a hydrogen atom, a methyl group, an acetylamino group or a ureido group. And m represents 2 or 3. ). 2. A method for dyeing a cellulosic fiber, comprising using the disazo compound according to claim 1.