JPS6347754B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention particularly relates to an azo dye suitable for reactive dyeing of cellulosic fiber materials. More specifically, the present invention provides the following general formula () in the form of a free acid: [In the formula, R is a hydrogen atom, X ₁ is a hydrogen atom, X ₂ is a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group, and D is the following formula (1), (2), (3) or (4) , (In the formula, n represents 1 or 2.) (In the formula, Acyl represents an acetyl group or a benzoyl group.) (In the formula, A is a methyl group or a carboxyl group,
B represents a hydroxyl group or an amino group, and E represents a sulfophenyl group, a disulfophenyl group, a chlorosulfophenyl group, a disulfonaphthyl group or a β-carboxyethyl group. ) (In the formula, G is a methyl group, J is a sulfonic acid group, a sulfomethyl group, or an aminocarbonyl group, and K is a hydrogen atom, a methyl group, or an ethyl group.) ] It is an azo dye shown by. It is well known that dyes having a group -SO ₂ CH ₂ CH ₂ OSO ₃ H or a monochlorotriazinyl group are used as reactive dyes for dyeing textile materials. The present inventors conducted a detailed study on the relationship between the structure and properties of this type of reactive dye, and found that the general formula ()
It has been found that the dyes give dyeings with excellent wet fastness, sunlight fastness and chlorine fastness in dyeing various textile materials, especially cellulosic textile materials. The azo dye () of the present invention can be produced, for example, as follows. General formula () (In the formula, R represents the above meaning.) An aminonaphthalene compound represented by the following is diazotized, and this is coupled with a coupling component represented by the general formula () HD () (wherein, D represents the above meaning). By coupling with, the general formula () (In the formula, R and D represent the above-mentioned meanings.) An azo compound represented by the following is obtained. Cyanuric chloride is primarily condensed to this azo compound (), and then the general formula () (In the formula, X ₁ and X ₂ represent the above-mentioned meanings.) The azo dye of the general formula () can be obtained by secondarily condensing the aniline compound represented by the following. Alternatively, an azo dye of the general formula () can be obtained by primary condensation of cyanuric chloride and an aniline compound represented by the general formula (), and then secondarily condensation of an azo compound of the general formula (). can be obtained. Alternatively, an aminonaphthalene compound of the general formula () and an aniline compound of the general formula () are condensed with cyanuric chloride in any order, and the general formula () (In the formula, R, X _{1 and} dye can be obtained. Alternatively, instead of the compound of general formula () (In the formula, X _{1 and} Azo dyes of formula () can be obtained. The coupling components represented by the general formula () are represented by the following formulas (i) to (iv). (i) Hydroxynaphthalene compounds (In the formula, n has the above meaning.) (ii) Aminohydroxynaphthalene compound (In the formula, Acyl has the above meaning.) (iii) Pyrazolone compound (In the formula, A, B and E have the above meanings.) (iv) Pyridone compound (In the formula, G, J and K have the above-mentioned meanings.) The following compounds can be mentioned as specific examples of the general formula (). 1-hydroxy-5-sulfonaphthalene, 1-
Hydroxy-3,6-disulfonaphthalene, 1-
Hydroxy-3,7-disulfonaphthalene, 1-
Hydroxy-3,7-disulfonaphthalene, 1-
Hydroxy-3,8-disulfonaphthalene, 1-
Hydroxy-4,6-disulfonaphthalene, 1-
Hydroxy-4,7-disulfonaphthalene, 1-
Hydroxy-4,8-disulfonaphthalene, 1-
Hydroxy-3,5-disulfonaphthalene, 1-
Hydroxy-8-benzoylamino-3,6-disulfonaphthalene, 1-hydroxy-8-benzoylamino-3,5-disulfonaphthalene, 1-
Hydroxy-8-ureido-3,6-dinaphthalene, 1-hydroxy-8-ureido-3,5-disulfonaphthalene, 1-hydroxy-8-acetylamino-3,6-disulfonaphthalene, 1-hydroxy- 8-acetylamino-3,5-disulfonaphthalene, 1-(2', 3', or 4'-sulfophenyl)-3-methyl-pyrazolone-5, 1-
(2′-chloro-4′ or 5′-sulfophenyl)-3
-Methylpyrazolone-5,1-(2'-methyl-
4'-sulfophenyl)-3-methylpyrazolone-
5,1-(2'-methyl-4'-sulfophenyl)-
3-carboxy-pyrazolone-5, 1-β-carboxyethyl-3-carboxy-pyrazolone-
5,1-[4',8-disulfonaphthyl-(2)]-3
-Methyl-pyrazolone-5,1-[5',7'-disulfonaphthyl(2)]-3-methyl-pyrazolone-
5,1-(2'-chloro-5'-sulfophenyl)-
3-methyl-5-aminopyrazole, 1-(2'-
Chlor-4'-sulfophenyl)-3-methyl-5
-Aminopyrazole, 1-(3' or 4'-sulfophenyl)-3-methyl-5-aminopyrazole, 1-carboxymethyl-3-methyl-pyrazolone-5, 1-β-carboxyethyl-3-methylpyrazolone- 5, 1-β-carboxyethyl-
3-methyl-5-aminopyrazole, 1-(4'-
sulfophenyl)-3-carboxy-pyrazolone-5, 3-cyano-4-methyl-6-hydroxypyridone, 1,4-dimethyl-3-cyano-6-
Hydroxypyridone, 1-ethyl-3-cyano-
4-methyl-6-hydroxypyridone, 1-propyl-3-cyano-4-methyl-6-hydroxypyridone, 3-aminocarbonyl-4-methyl-
6-hydroxypyridone, 1,4-dimethyl-3
-aminocarbonyl-6-hydroxypyridone,
1-ethyl-3-aminocarbonyl-4-methyl-6-hydroxypyridone, 1-propyl-3-
Aminocarbonyl-4-methyl-6-hydroxypyridone, 4-methyl-6-hydroxypyridone-3-sulfonic acid, 1,4-dimethyl-6-hydroxypyridone-3-sulfonic acid, 1-ethyl-
4-methyl-6-hydroxypyridone-3-sulfonic acid, 1-propyl-4-methyl-6-hydroxypyridone-3-sulfonic acid, 3-sulfomethyl-4-methyl-6-hydroxypyridone, 1,
4-dimethyl-3-sulfomethyl-6-hydroxypyridone, 1-ethyl-3-sulfomethyl-4
-Methyl-6-hydroxypyridone, 1-propyl-3-sulfomethyl-4-methyl-6-hydroxypyridone and 5-carboxylic acid amide substituted products thereof. Examples of the aniline compound of general formula (v) include the following compounds. 1-Aminobenzene-2-, -3- or -4
-β-sulfatoethylsulfone, 1-amino-
4-Methylbenzene-3-β-sulfatoethylsulfone, 1-amino-4-methoxybenzene-
3-β-sulfatoethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone
2-sulfonic acid, 1-aminobenzene-5-β-
Sulfatoethylsulfone-2-sulfonic acid, 1
-Amino-2-methoxybenzene-5-β-sulfatoethylsulfone, the dyes of the invention can be used in a wide variety of materials having hydroxyl or amino groups, in particular textile materials such as wool, silk, synthetic polyamides and natural or recycled materials. Cellulose, for example cotton or viscose rayon materials, can be dyed according to conventional methods carried out using water-soluble reactive dyes. For example, in the case of cellulosic fibers, dyeing is carried out using the dye according to the invention and an acid binder such as caustic soda, sodium carbonate, phosphate, silicate or sodium bicarbonate. The dyeing method can be selected depending on the properties and physical shape of the fiber, such as exhaust method,
A textile printing method or a cold-patch batch-up method can be used. In the case of the exhaust method, it 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 sodium carbonate, trisodium phosphate, or caustic soda. In the case of printing processes, thickening agents or emulsifying thickening agents such as, for example, sodium alginate or starch ethers and sodium carbonate, sodium bicarbonate, caustic soda, sodium triphosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds are used. applied to the fibers together with an alkaline or alkali-releasing agent, 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 applying it to. In the case of cold-patch batch-up dyeing, use caustic soda alone or sodium silicate as the acid binder.
Using sodium carbonate or trisodium phosphate in combination, and in some cases adding mirabilite or common salt, and adding a solubilizing agent or penetrating agent such as urea if desired, it is applied to the fibers at around room temperature. patsuded to,
It can be dyed by winding it up into a roll, leaving it for 3 hours or overnight, washing it with water, and drying it. The dyed cellulose fiber thus obtained has good wet fastness, sunlight fastness and chlorine fastness, and also good discharge printability. Furthermore, the dye of the present invention has high fiber reactivity,
It also has good fixing properties and gives dyed products with extremely high color density at relatively low temperatures. The present invention will be explained by way of examples. In the text, parts indicate parts by weight. Example 1 25.2 parts of 2-amino-1-sulfo-5-aminomethylnaphthalene was added to 400 parts of ice water, and 21 parts by volume of concentrated hydrochloric acid were added. Then 21 parts by volume of 35% sodium nitrite solution are added dropwise. At the end of the addition, the diazotized product precipitated. On the other hand, 1-hydroxy-8-acetylamino-
36.1 parts of 3,6-disulfonaphthalene are dissolved in 300 parts of water, the solution is cooled by adding ice and 28 parts of sodium bicarbonate are added. This suspension is added to the diazotization solution to perform a coupling reaction. After the coupling is completed, the precipitated dye is separated,
Add 1000 parts by volume of ice water and adjust the pH to 6. 18.4 parts of cyanuric chloride is added to this solution at 0°C, and the pH is kept constant by adding 2N caustic soda solution. After the reaction was completed, a solution consisting of 100 parts of water and 28 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, the pH was adjusted to 5 ± 0.5, and the temperature was raised to 30
Increase temperature to ~35°C. After the reaction was completed, sodium chloride was added to precipitate crystals, followed by suction filtration to separate the dye. After separation, a powder was obtained which dissolves in water and gives a clear red color. This dye has the following structure as the free acid. [Dyeing Example] 0.3 parts of dye (1) prepared according to Example 1 are dissolved in 200 parts of water. After adding 10 parts of cotton to this, the temperature was raised to 60℃ over 10 minutes, and then anhydrous sodium sulfate was added.
20 parts were added and staining continued for 30 minutes. Next, 4 parts of anhydrous sodium carbonate was added to this, and staining was carried out at 60°C for 60 minutes. Next, wash with water and soap. A bright red dyeing is obtained which has outstanding stability against moisture, sunlight and the effects of chlorine. In the table below, instead of 1-hydroxy-8-acetylamino-3,6-disulfonaphthalene,
Example except that an equivalent amount of the azo component in the first column is used, and an equivalent amount of aminoaryl-β-sulfatoethyl sulfone in the second column is used instead of 1-amino-3-β-sulfatoethyl sulfone. By following method 1, useful dyes having the hues indicated in the right column were obtained.

【table】

[Table] Example 2 25.2 parts of 2-amino-1-sulfo-5-aminonaphthalene is dissolved in 300 parts of water at pH 6. Add 18.4 parts of cyanuric chloride at 0°C and keep the pH constant by adding 2N caustic soda solution.
After the reaction is complete, a solution of 7 parts of sodium nitrite in 50 parts of water is added and poured into 25 parts of concentrated hydrochloric acid and 100 parts of crushed ice.
After 1 hour, excess nitrous acid is decomposed and removed by sulfamic acid. The diazo solution obtained in this way has 1-
Add 25.4 parts of (3'-sulfophenyl)-3-methylpyrazolone-(5) and adjust the pH to 5±1 with 2N caustic soda solution. After the cupping is finished, water
A solution consisting of 100 parts and 28 parts of 1-aminobenzene-3-β-sulfatoethylsulfone is added.
Adjust the pH to 5±0.5 and raise the temperature to 30-35°C. After the reaction was completed, 70 parts of sodium chloride was added to precipitate crystals, which were then filtered by suction, washed, and heated at 60°C.
Dry with. A dye that dissolves in water turns yellow.
This dye has the following compositional structure as a free acid. [Dyeing example] Dissolve 0.3 parts of the above dye (13) in 200 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50°C.
After 20 minutes, add 4 parts of soda. Dye for 1 hour at that temperature. After dyeing, washing and soaping were performed to obtain a yellow dyed product with good fastness properties. Similarly, 1-aminobenzene-3-β of Example 2
- Table 2 instead of sulfate ethyl sulfone
The compound in the column is 1-(3′-sulfophenyl)
-3-Methylpyrazolone- (5) If an azo component in the column of Table 2 is used, useful dyes giving the hues shown in the right column can be obtained.

【table】

[Table] Example 3 25.2 parts of 2-amino-1-sulfo-5-aminomethylnaphthalene is dissolved in 300 parts of water at pH 6.
Add 18.4 parts of cyanuric chloride at 0°C, and keep the pH constant by adding 2N caustic soda solution.
After the reaction is complete, add 100 parts of water and 1-aminobenzene-3.
-Add 28 parts of β-sulfatoethyl sulfone, adjust the pH to 5±0.5, and raise the temperature to 30-35°C. After the reaction is complete, a solution consisting of 7 parts of sodium nitrite and 50 parts of water is added and poured into 25 parts of concentrated hydrochloric acid and 100 parts of crushed ice. After 1 hour, excess nitrous acid is decomposed and removed by sulfamic acid. 200 parts of water and 1,4
A solution consisting of 21 parts of -dimethyl-3-sulfo-6-hydroxypyrid-2-one is poured into the diazo solution. Add sodium carbonate solution dropwise and adjust the PH value to 3.5. After the coupling was completed, sodium chloride was added to precipitate crystals, which were then filtered under suction to separate the dye. This dye has the following structure in free acid form. When this dye is dyed in the same manner as the dye of Example 1, a bright yellow dyeing with a green tint is obtained which has wet and sunlight fastness properties. Similarly, in place of 1,4-dimethyl-3-sulfo-6-hydroxypyrid-2-one in Example 3, the azo component in the column of Table 3 was used. Use of the compounds in the columns in place of fat ethyl sulfone also yields useful dyes that give the hues shown in the right column.

【table】

【table】

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: [In the formula, R is a hydrogen atom, X ₁ is a hydrogen atom, X ₂ is a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group, and D is a ), (In the formula, n represents 1 or 2.) (In the formula, Acyl represents an acetyl group or a benzoyl group.) (In the formula, A is a methyl group or a carboxyl group,
B represents a hydroxyl group or an amino group, and E represents a sulfophenyl group, a disulfophenyl group, a chlorosulfophenyl group, a disulfonaphthyl group or a β-carboxyethyl group. ), (In the formula, G is a methyl group, J is a sulfonic acid group, a sulfomethyl group, or an aminocarbonyl group, and K is a hydrogen atom, a methyl group, or an ethyl group.) ] Azo dye shown by. 2. The dye according to claim 1, which is used for cellulose fibers.