JPH0217590B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers from gray to black. More specifically, the present invention includes:
The general formula below in the free acid form () (In the formula, R ₁ and R ₂ are each a hydrogen atom or C ₁ to ₄
an alkyl group, Y is a fluorine atom or a chlorine atom, n
represents 0 or 1. Ring A represents a benzene ring or a naphthalene ring, which may have a substituent selected from a nitro group and a sulfonic acid group. M is chromium () ion or cobalt () ion, X is the formula -SO ₂ CH ₂ CH ₂ Cl, -
SO ₂ CH=CH ₂ , ―SO ₂ CH ₂ CH ₂ OSO ₃ H, ―
SO ₂ CH ₂ CH ₂ OSO ₃ H ₂ or -N(R ₃ )
In the SO ₂ CH ₂ CH ₂ OSO ₃ H group, R ₃ represents a hydrogen atom, a methyl group or an ethyl group. In addition to X, ring B includes a lower alkyl group, a lower alkoxy group, a chlorine atom,
A benzene ring which may be substituted with one or two substituents selected from a bromine atom, a sulfonic acid group and a carboxylic acid group, or a naphthalene ring which may be substituted with one sulfonic acid group in addition to X. represent ) This is a method for dyeing cellulose fibers, which is characterized by using the dye shown in the following. A benzene-based or naphthalene-based diazonium compound and 1-hydroxynaphthylamine sulfonic acids are coupled, and Cr is used as a metallizing agent.
1:2 type metal complex dyes obtained using Co() or Co() are already known to dye textile materials from gray to black. Among these dyes, dyes having a monohalogenotriazinyl group are well known as reactive dyes. However, these reactive dyes generally require high dyeing temperatures and lack suitability for exhaust dyeing, so they are only used for textile printing.Furthermore, they have the disadvantage of low acid stability of the dyed products obtained. Therefore, it could never be said to be sufficient for practical purposes. On the other hand, it is known that dyes having a β-sulfatoethylsulfonyl group can be applied to dyeing textile materials as so-called vinylsulfone type reactive dyes. However, dyed products using azo gray to black reactive dyes having a β-sulfatoethylsulfonyl group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. For these reasons, the present inventors have found that the chlorine fastness is particularly excellent, and furthermore, the light fastness is sufficient.
As a result of extensive research in search of a gray to black vinyl sulfone type reactive dye with sweat and sunlight fastness, we found that the dye represented by the above general formula (), i.e., a vinyl sulfonyl group or its precursor substituted as a reactive group. It has been found that disazo dyes having monochloro or monofluorotriazinyl groups give gray to black dyeings meeting these conditions. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having monochloro or monofluorotriazinyl groups as described above. In the present invention, examples of cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton. In the case of the exhaust method, the dyeing of the present invention uses soda carbonate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as tribasic sodium phosphate or caustic soda. In the case of printing, pastes such as, for example, sodium alginate, starch ethers or emulsifying pastes, and sodium carbonate, bicarbonate, caustic soda, tribasic sodium phosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds are used. applied to the fibers together with alkaline or alkali-releasing agents, optionally with the addition of customary printing aids or dispersants, such as urea, dried and heat treated, especially in the presence of water vapor. It can be dyed by attaching it. In the case of cold batch dyeing, caustic soda alone or in combination with sodium silicate, soda carbonate, or sodium phosphate is used as an acid binder, and if necessary, mirabilite or common salt is added, and if desired, a dissolving agent such as urea is used. Alternatively, it is padded onto the fibers at room temperature with the addition of a penetrant and rolled up into a roll.
After leaving it for an hour or overnight, it can be dyed by drying with water. The dye of the present invention can be produced, for example, as follows. General formula () (In the formula, n and R ₁ have the above-mentioned meanings.) A 1-hydroxynaphthylamine sulfonic acid compound represented by the general formula () (In the formula, A has the above meaning) is coupled with a diazonium compound, and then chromium () salt or cobalt () salt is added and maintained at 70 to 105°C to obtain a 1:2 type complex salt dye, This and the general formula () (In the formula, R ₂ , B and X have the above-mentioned meanings.) (In the formula, Y has the above-mentioned meaning) It can be obtained by condensation with 2,4,6-trihalogeno-s-triazine shown in the following in any order. Examples of the 1-hydroxynaphthylamine sulfonic acid compound represented by the general formula () that can be used in the present invention include 1-hydroxy-8-aminonaphthalene-3,5- or -3,6-disulfonic acid, 1-hydroxy-7 -aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-6
-or-7-aminonaphthalene-3-sulfonic acid or 1-hydroxy-6-or-7-N
-Methylaminonaphthalene-3-sulfonic acid. Examples of the diazonium compound represented by the general formula () include 6-nitro-1-diazonio-
4-sulfo-2-naphthrate, 4- or 5-
Nitro-1-diazonio-2-phenolate is mentioned. Examples of the chromium salt used as a metallizing agent include chromium sulfate, chromium salicylate, chromium formate, and chromium oxide. Examples of cobalt () salts include cobalt sulfate and cobalt acetate. Examples of the amine represented by the general formula () include the following. 1-aminobenzene-2-, -3- or -4-β-sulfatoethylsulfone, 1-aminobenzene-3-β-phosphatoethylsulfone, 1-amino-4-methylbenzene-3-β- sulfatoethyl sulfone,
1-aminobenzene-3-β-chloroethylsulfone, 1-amino-4-methoxybenzene-3-
β-sulfatoethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone-2-
Sulfonic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2-sulfonic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2,4-disulfonic acid, 1-aminonaphthalene- 4-β-sulfatoethylsulfone, 1-amino-2,5-dimethoxybenzene-4-β-sulfatoethylsulfone, 1-aminobenzene-
4-β-sulfatoethylsulfone-2-carboxylic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2-carboxylic acid, 1-amino-
2-methoxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-chlorobenzene-
4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-
Sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy- 5-methylbenzene-4-β-sulfatoethylsulfone, 1-amino-2,5-diethoxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-β-
Sulfatoethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 1-aminobenzene-5-vinylsulfone-2,4-disulfonic acid, 1-aminobenzene-5-β-phosphatoethylsulfone -2,4-disulfonic acid, 1-
Aminobenzene-5-β-chloroethylsulfone-2,4-disulfonic acid, 2-aminonaphthalene-8-β-phosphatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-vinylsulfone-6-sulfone Acid, 1-amino-2-methoxy-5-methylbenzene-4-β-chloroethylsulfone, 2-aminophenol-4-β-sulfatoethylsulfone, 1-aminobenzene-
3- or -4-vinylsulfone, 1-amino-
2-hydroxybenzene-4-β-sulfatoethylsulfone, 1-aminobenzene-5-vinylsulfone-2-sulfonic acid, 3-(N-methyl-
β-sulfatoethylsulfonylamino)-1-
Aminobenzene, 3-(N-ethyl-β-sulfatoethylsulfonylamino)-1-aminobenzene, 3-β-sulfatoethylsulfonylamino-1-aminobenzene, 1-(N-methylamino)benzene -2-3- or -4-β-sulfatoethylsulfone, 1-(N-methylamino)benzene-3-β-phosphateethylsulfone, 1-(N-methylamino)-4-methoxybenzene- 3-β-sulfatoethylsulfone, 1-(N-methylamino)naphthalene-4-
β-sulfatoethylsulfone, 2-(N-methylamino)naphthalene-8-β-sulfatoethylsulfone, 1-(N-ethylamino)benzene-2-, -3- or -4-β -Sulfatoethylsulfone, 1-(N-ethylamino)
Benzene-3-β-phosphatoethylsulfone, 1-(N-ethylamino)-4-methoxybenzene-3-β-sulfatoethylsulfone,
1-(N-ethylamino)naphthalene-4-β-
Sulfatoethylsulfone, 2-(N-ethylamino)naphthalene-8-β-sulfatoethylsulfone. The thus obtained dye of the present invention has particularly high chlorine fastness, light fastness, perspiration, sunlight, Excellent robustness. Excellent light fastness, sweat fastness and sunlight fastness
Suitable for dyeing external wear such as sportswear. Furthermore, since the dye of the present invention exhibits a high exhaustion rate, it is possible not only to obtain dyed products with high density, but also to have an advantage in terms of wastewater treatment since only a small amount of dye remains in the dye bath. has advantages. In the present invention, particularly by mixing a 1:2-type chromium complex dye and a 1:2-type cobalt complex dye, a dyed product with favorable hue can be obtained. As a dye similar to the dye of the present invention, for example, Japanese Patent Publication No. 36-15632 describes The dye shown is described. However, the acid stability of dyed products obtained using this dye (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes,
at a temperature of 37 ± 2 °C using a bar spirometer.
(treated at 125 g/cm ² for 6 hours) is inferior to the dye-dyed products of the present invention, and has the disadvantages of requiring a high dyeing temperature and having unsatisfactory exhaust dyeability. Therefore, it cannot be said to be sufficient in practical terms. Furthermore, the dye of the present invention has excellent wash-off properties, and has the great advantage that unfixed dye can be easily removed. Furthermore, the dye of the present invention has the unique ability to be hardly affected by changes in dyeing temperature, alkali agent, inorganic salt addition amount, and bath ratio during exhaust dyeing, and allows dyeing to be carried out with extremely high reproducibility. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 Formula (1) Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, add 10 parts of cotton, and raise the temperature to 50°C. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a dyed product with excellent fastness and a high concentration of gray band edges. Reference example 1 [Synthesis example of dye (1) of Example 1] 1-Hydroxy-6-aminonaphthalene-3-
6-nitro-1-diazonio-
Add 18.6 parts of 4-sulfo-2-naphthrate to 15
Stir overnight at ~25 °C. After adjusting the pH to 8.0 to 8.5 with hydrochloric acid, add chromium salicylate to 1.3 in terms of chromium content.
The mixture is heated at 80 to 85°C for about 3 hours, and during this time the pH is maintained at 8.0 to 8.5 using 2N-NaOH. 0-5
After cooling to ℃, 8.9 parts of cyanuric chloride was added, and the pH was maintained at 5.5 to 6.5 using a 20% aqueous sodium carbonate solution.
Stir for ~1.5 hours. followed by 1-aminobenzene-3-β-sulfatoethylsulfone 13.6
Add 20% sodium carbonate aqueous solution to adjust the pH to 4-6.
Keep warm at 30-35℃ for 3-4 hours. After the reaction was completed, the pH was adjusted to 5 to 5.5 and spray-dried to obtain 53.7 parts of dye (1). Example 2 Formula (2) A gray-brown dyed product with excellent fastness was obtained by dyeing using the dye shown in the method described in Example 1. Example 3 8 parts of the dye of formula (1) and 2 parts of the dye of formula (2) were mixed, 0.8 part of them was dissolved in 200 parts of water, 20 parts of mirabilite was added, and 10 parts of cotton was added to give 50 parts of the dye. Increase temperature to ℃. Then 30
After a few minutes have elapsed, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a black dyed product with excellent fastness. Examples 4 to 37 In Example 1, the following 4 to 37 were used instead of dye (1).
Dyeing was carried out in the same manner except that the following dye was used. A dense gray to black dyeing with excellent fastness properties was obtained. The following dyes have a diazo component [the above general formula ()] =
Column A, coupling component [the above general formula ()] = B
Column, metal imparting agent = Column C, 2,4,6-trihalogeno-s-triazine = Column D, amine [the above general formula ()] = Column E, and [color tone of 1:2 type metal complex dye on ceruse material ]=Characterized by column F.

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Claims (1)

[Claims] 1 The following general formula in the form of a free acid: (In the formula, R ₁ and R ₂ are each a hydrogen atom or C ₁ to ₄
an alkyl group, Y is a fluorine atom or a chlorine atom, n
represents 0 or 1. Ring A represents a benzene ring or a naphthalene ring, which may have a substituent selected from a nitro group and a sulfonic acid group. M is chromium () ion or cobalt () ion, X is the formula -SO ₂ CH ₂ CH ₂ Cl, -
SO ₂ CH=CH ₂ , ―SO ₂ CH ₂ CH ₂ OSO ₃ H, ―
SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or -N(R ₃ )
In the SO ₂ CH ₂ CH ₂ OSO ₃ H group, R ₃ represents a hydrogen atom, a methyl group or an ethyl group. In addition to X, ring B includes a lower alkyl group, a lower alkoxy group, a chlorine atom,
A benzene ring which may be substituted with one or two substituents selected from a bromine atom, a sulfonic acid group and a carboxylic acid group, or a naphthalene ring which may be substituted with one sulfonic acid group in addition to X. represent ) A method for dyeing cellulose fibers, characterized by using a dye represented by: