JPH0217588B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers yellow. More specifically, the present invention provides the following general formula () in the form of a dilute acid: [In the formula, D is the formula (Here, R ₁ is a hydroxy group or amino group, R ₂ is a methyl group or carboxyl group, R ₃
represents a phenyl group substituted with 1 to 3 groups selected from chlorine, methyl group, sulfonic acid group and amino group, or a naphthyl group substituted with these groups. ) pyrazolone derivative residue or formula (Here, R ₄ is a cyano group, a carbamoyl group,
R 5 represents a sulfomethyl group or a sulfonic acid group, and R ₅ represents hydrogen or a C ₁ to C ₃ alkyl group, respectively. ) represents a 6-hydroxy-2-pyridone derivative residue. X ₁ and X ₂ are hydrogen, chlorine, and
Represents a methyl group, methoxy group, carboxyl group or sulfonic acid group. ] This is a method for dyeing cellulose fibers, which is characterized by using the dye shown below. It is known that dyes having a β-sulfatoethyl sulfone group can be applied as so-called vinyl sulfone type reactive dyes for dyeing textile materials. However, dyeings made with azo-based yellow reactive dyes having a β-sulfatoethyl sulfone group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. There is a strong demand for a yellow reactive dye with excellent strength. Yellow dyes with a monochlorotriazinyl group as another typical reactive group different from the β-sulfatoethyl sulfone group are also known, but these reactive dyes generally require high dyeing temperatures. However, since it lacks suitability for exhaust dyes, it is only used for textile printing, and the resulting dyed product has the disadvantage of low acid stability, so it is by no means sufficient for practical use. Nakatsuta. For this reason, the present inventors conducted extensive research in search of a yellow vinyl sulfone type reactive dye with particularly excellent chlorine fastness. - It has been found that monoazo dyes having a sulfatoethylsulfone group and a monohalogenotriazinyl group give yellow dyeings with excellent chlorine fastness. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above. In the present invention, the 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 is carried out at a relatively low temperature in a dye bath containing Glauber's salt or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda. It can also be dyed using a textile printing method. The dye of the present invention can be produced, for example, as follows. A dichlortriazinyl compound is obtained by primary condensation of naphthotriazole and cyanuric chloride, diazotized, and coupled with a pyrazolone derivative or pyridone derivative. (wherein D has the meaning given above) is obtained. Then the general formula () [In the formula, X ₁ and X ₂ have the above-mentioned meanings] The dye represented by the general formula () can be obtained by secondarily condensing the aniline compound represented by the following. Alternatively, by condensing cyanuric chloride with a naphthotriazole represented by the formula () and an aniline compound represented by the general formula () in any order, (wherein X ₁ and X ₂ have the above-mentioned meanings) to obtain a monochlorotriazinyl compound,
The dye of the general formula () can also be obtained by diazotizing and coupling with a pyrazolone derivative or a pyridone derivative. Alternatively, the general expression () [In the formula, X _{1 and} A dye of general formula () may be obtained by esterification in a dye. In the general formula (), examples of the coupling component D include the following compounds. (i) Pyrazolone derivative 1-(2', 3' or 4'-chlorophenyl)-3
-Methylpyrazolone-5 1-(2', 3' or 4'-sulfophenyl)-3
-Methylpyrazolone-5 1-(2'-methyl-4'-sulfophenyl)-3
-Methylpyrazolone-5 1-(2'-chloro-4'-sulfophenyl)-3
-Methylpyrazolone-5 1-(2',5'-dichloro-4'-sulfophenyl)
-3-methylpyrazolone-5-4'-sulfophenyl)-3-methylpyrazolone-5 1-(2',4'-disulfophenyl)-3-methylpyrazolone-5 1-(2',5'-disulfophenyl)- 3-Methylpyrazolone-5 1-[5',7'-disulfonaphthyl-(2')]-3
-Methylpyrazolone-5 1-(3'-aminophenyl)-3-methylpyrazolone-5 1-[6'-sulfonaphthyl-(2')]-3-methylpyrazolone-5 1-(2'-methyl-3 '-amino-5'-sulfophenyl)-3-methylpyrazolone-5 1-[4',7'-disulfonaphthyl-(2')]-3
-Methylpyrazolone-5 1-(2'-sulfo-4'-aminophenyl)-3
-Methylpyrazolone-5 1-(4'-sulfo-3'-aminophenyl)-3
-Methylpyrazolone-5 and the corresponding 3-carboxy derivative 1-(4'-sulfophenyl)-3-methyl-5-
Aminopyrazole 1-(3'-sulfophenyl)-3-methyl-5
-Aminopyrazole (ii) 6-hydroxy-2-pyridone derivative 3-cyano-4-methyl-6-hydroxy-2
-Pyridone 1,4-dimethyl-3-cyano-6-hydroxy-2-pyridone 1-ethyl-3-cyano-4-methyl-6-hydroxy-2-pyridone 1-propyl-3-cyano-4-methyl- 6-
Hydroxy-2-pyridone 3-aminocarbonyl-4-methyl-6-hydroxy-2-pyridone 1,4-dimethyl-3-aminocarbonyl-6
-Hydroxy-2-pyridone 1-ethyl-3-aminocarbonyl-4-methyl-6-hydroxy-2-pyridone 1-propyl-3-aminocarbonyl-4-methyl-6-hydroxy-2-pyridone 3-sulfomethyl- 4-Methyl-6-hydroxy-2-pyridone 1,4-dimethyl-3-sulfomethyl-6-hydroxy-2-pyridone 1-ethyl-3-sulfomethyl-4-methyl-
6-hydroxy-2-pyridone 1-propyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone 3-sulfo-4-methyl-6-hydroxy-2
-Pyridone 1,4-dimethyl-3-sulfo-6-hydroxy-2-pyridone 1-ethyl-3-sulfo-4-methyl-6-hydroxy-2-pyridone 1-propyl-3-sulfo-4-methyl- 6-
Hydroxy-2-pyridone 1,4-dimethyl-3-sulfomethyl-5-aminocarbonyl-6-hydroxy-2-pyridone 1-ethyl-3-sulfomethyl-4-methyl-
5-Aminocarbonyl-6-hydroxy-2-pyridone Examples of the compound of general formula () include the following compounds. 1-aminobenzene-2,3 or 4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone, 1-amino-4-methoxybenzene-3-
β-sulfatoethylsulfone, 1-amino-
2-Methoxy-5-methylbenzene-4-β-sulfatoethylsulfone, 1-amino-2-sulfobenzene-4-β-sulfatoethylsulfone, 1-amino-2-sulfobenzene-5-β
-Sulfate ethyl sulfone, 1-amino-2
-Carboxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-chlorobenzene-3- or 4-β-sulfatoethylsulfone. The dye of the present invention thus obtained has excellent chlorine fastness, light fastness, and sweat/sunlight fastness. Especially considering that the use of chlorine bleach in household laundry has recently become widespread, the value of the dye of the present invention, which has excellent chlorine fastness, is high. In addition, its excellent light fastness, sweat fastness and sunlight fastness make it 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 excellent wash-off properties, which has the great advantage that unfixed dye can be easily removed. are doing. As a dye similar to the present invention, for example,
Publication No. 39-18184 states the following: The yellow reactive dye shown is described. However, the chlorine fastness of these dyes is very low, being grade 1 according to the ISO method, and their practical value is small. On the other hand, the yellow dye of the present invention has an excellent chlorine fastness of 2nd to 3rd grade or 3rd grade according to the ISO method.
In addition, the light fastness is 6th grade, and the sweat and sunlight fastness is 4th grade or 4th to 5th grade, both of which are excellent. Furthermore, the acid stability of the dyed product (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes and then treat it at 125g/ ^cm2 for 6 hours at a temperature of 37±2℃ using a bar spirometer) is 4 to 4. It is good at grade 5 to grade 5. Furthermore, the dye of the present invention has the unique ability to be hardly affected by changes in the 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 mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 50℃.
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 yielded a yellow dyed product with excellent fastness, especially fastness to chlorine. The above dye is synthesized, for example, as follows. To a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 10°C. A solution prepared by dissolving 25.7 parts of the naphthotriazole compound of formula () in 150 parts of water at a pH of 7 to 8 is added dropwise to the solution at 0 to 5°C over 1 hour. After stirring at the same temperature for 2 hours, a 20% aqueous sodium carbonate solution was added to adjust the pH to 7-8. Next, 3.5 parts of sodium nitrite is added and dissolved, and 12.7 parts of concentrated hydrochloric acid is injected at 0 to 5°C to diazotize. This diazo suspension was mixed with 1,4-dimethyl-6-hydroxy-3
Add 10.5 parts of sulfomethyl-2-pyridone to 100 parts of 1N sodium hydroxide solution, add 5 parts of sodium bicarbonate, and stir until coupling is complete. Then, 16.9 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the temperature was raised to 40°C while adjusting the pH to 5 to 6, and the mixture was stirred at the same temperature for 5 hours. 60 parts of sodium chloride was added to this solution to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (1). Example 2 Formula (2) Dissolve 0.3 parts of the dye shown in 200 parts of water and add mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 60℃.
Then, after 20 minutes, 3 parts of tribasic sodium phosphate is added. Dye for 1 hour at that temperature. After dyeing, washing with water and soaping yielded a yellow dyed product with excellent fastness, especially fastness to chlorine. Example 3 In the same manner as Example 1 or Example 2, the following D
When dyeing was carried out using dyes obtained using the general formula (2) and (2) as ingredients, yellow dyed products with excellent chlorine fastness were obtained in both cases.

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Claims (1)

[Claims] 1 The following general formula in the form of a free acid: [In the formula, D is the formula (Here, R ₁ is a hydroxy group or amino group, R ₂ is a methyl group or carboxyl group, R ₃
represents a phenyl group substituted with 1 to 3 groups selected from chlorine, methyl group, sulfonic acid group and amino group, or a naphthyl group substituted with these groups. ) pyrazolone derivative residue or formula (Here, R ₄ is a cyano group, a carbamoyl group,
R 5 represents a sulfomethyl group or a sulfonic acid group, and R ₅ represents hydrogen or a C ₁ to C ₃ alkyl group, respectively. ) represents a 6-hydroxy-2-pyridone derivative residue. X ₁ and X ₂ are hydrogen, chlorine, and
Represents a methyl group, methoxy group, carboxyl group or sulfonic acid group. ] A method for dyeing cellulose fibers, characterized by using the dye shown below.