JPH042630B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing a bisazo-reactive dye represented by the following general formula () in the form of a free acid. [In the formula, D may have one or two substituents selected from a _C1 to _C4 alkyl group, a _C1 to _C4 alkoxy group, a nitro group, a halogen, and a sulfonic acid group. represents a good phenylene group or an optionally substituted β-naphthylene group, and Q is -
SO ₂ CH=CH ₂ or −SO ₂ CH ₂ CH ₂ R (here R
represents a group that is eliminated by the action of an alkali), and X represents a hydrogen atom or a sulfonic acid group. ] Conventionally, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (hereinafter referred to as H acid)
A bisazo dye represented by the following formula (A) consisting of and two types of diazo compounds. [In the formula, D ₁ represents an optionally substituted phenylene or naphthylene group, D ₂ represents an optionally substituted phenyl or naphthyl group, and Q has the above meaning. ] First, the following formula (B), (C) Q-D ₁ -NH ₂ (B) D ₂ -NH ₂ (C) [D ₁ , D ₂ and Q have the above-mentioned meanings. ] Of the aromatic amines shown, (B) is diazotized,
This is carried out by coupling H acid in an acidic medium, and then coupling the obtained monoazo compound with a diazotized product obtained by diazotizing the aromatic amine (C). This method is disclosed in, for example, Japanese Patent Publication No. 43-15299, Japanese Patent Publication No. 45-4337,
Alternatively, as described in JP-A-57-44667, it has been widely employed in the production of this type of bisazo dye. However, in this method, it is necessary to separately diazotize two types of aromatic amines twice, and in addition, H acid and two types of diazo compounds are added sequentially to couple in two stages. When the first diazo compound is introduced, if the first-stage coupling is not completed, an undesired bisazo dye will be produced, resulting in a decrease in yield and quality, resulting in operational complexity and reaction management problems. Difficulty has been pointed out as a problem. On the other hand, CIReactive Black5, a bisazo dye often used for dyeing cellulose fibers, is
It is well known that it can be produced by mixing diazotized products of 1-aminobenzene-4-β-sulfatoethylsulfone in a molar ratio and coupling by adding an acid binder. When this method is applied to the production of the bisazo dye represented by the above formula (A), that is, when the amines represented by the formulas (B) and (C) are simultaneously diazotized and coupled with H acid, the desired formula In addition to the dye represented by (A), as a by-product, naturally in the form of a free acid, the following formula The bisazo compound represented by is produced in a considerable proportion, causing serious problems in terms of yield and quality. As a means to avoid such problems, as mentioned above, one aromatic amine is diazotized to form a monoazo compound coupled with H acid, and then another aromatic amine is diazotized and coupled with this. This is why the production method of bisazo dyes has been used for a long time. Under these circumstances, the present inventors have conducted intensive studies to find an industrially advantageous manufacturing method for this type of bisazo dye that does not have the above-mentioned operational complexity, quality, and reaction control difficulties. As a result, if the types of aromatic amines used are carefully selected and combined in a specific manner, even if each aromatic amine is mixed and diazotized at the same time, and then coupled with H acid, the above (D),
Almost no by-products corresponding to the bisazo compounds represented by (E) and (F) are produced, and the target bisazo dye represented by the above general formula () has excellent selectivity, and there are no problems in terms of yield and quality. The present inventors have now completed the present invention by discovering that the bisazo dye obtained by such a specific combination has extremely excellent dye properties. That is, in producing the bisazo reactive dye represented by the general formula (), the present invention provides the following general formula () Q-D-NH ₂ () [wherein D and Q have the above-mentioned meanings]. ] Aromatic amines represented by and the following general formula () [In the formula, X has the above meaning. ] The above general formula () is characterized in that a diazo compound in which multiple types coexist, obtained by mixing 2-naphthylamine-1-sulfonic acids represented by the formula and simultaneously diazotizing the mixture, is coupled with H acid or a salt thereof. The present invention provides a method for producing a bisazo-reactive dye shown in the following. In the dye of the general formula () which is the object of the present invention, the group R that is eliminated by the action of an alkali is, for example, a halogen atom such as a hydrogen atom or a bromine atom, an ester group of an organic carboxylic acid or a sulfonic acid such as an acetyloxy residue, etc. lower alkanoyloxy residue,
benzoyloxy residue or benzenesulfonyloxy group or free acid form with the formula −OPO ₃ H ₂ −
It is an acidic ester group of phosphoric acid or sulfuric acid represented by SSO ₃ H or -OSO ₃ H, and when removed by the action of an alkali, the group -SO ₂ CH ₂ CH ₂ R is converted to a vinylsulfonyl group. Among these, particularly preferred are acidic ester groups of sulfuric acid, that is, as Q, the group -SO ₂ CH ₂ CH ₂ OSO ₃ H is preferred. The method of the present invention will be explained in detail below. Examples of aromatic amines in which D is a phenylene group in 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-sulfatoethylsulfone, 1-aminobenzene-3-
β-chloroethylsulfone, 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone, 1-amino-2,5-dimethoxybenzene-4-β-sulfatoethylsulfone, 1-amino- 2-methoxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-chlorobenzene-4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene-5-β-sulfato Ethylsulfone, 1-amino-2,5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-β-
Sulfatoethylsulfone, 1-amino-2-bromobenzene-4-β-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methyl benzene-4-β-chloroethylsulfone,
1-Aminobenzene-2-, -8- or -4-
Vinyl sulfone, 1-amino-2-nitrobenzene-4-β-sulfatoethyl sulfone, 1-
Amino-2-sulfo-4 or 5-β-sulfatoethylsulfone, 1-amino-2-methoxy-
5-chlorobenzene-4-β-sulfatoethylsulfone and -4-β-vinylsulfone, 1
-amino-2-ethoxy-5-chlorobenzene-
4-β-sulfatoethyl sulfone and -4
-β-vinylsulfone, 5-chloroaniline-2
-β-sulfatoethylsulfone, 5-sulfoaniline-2-β-sulfatoethylsulfone, aniline-2-β-thiosulfatoethylsulfone, 5-chloroaniline-2-β-thiosulfate Ethyl sulfone, 5-sulfoaniline-2-β-thiosulfatoethyl sulfone, aniline-2-β-phosphatoethyl sulfone,
5-Chloraniline-2-β-phosphatoethylsulfone, 5-sulfoaniline-2-β-phosphatoethylsulfone, aniline-2-vinylsulfone, 5-chloroaniline-2-vinylsulfone, 5-sulfoaniline- 2-vinylsulfone, aniline-2-β-chloroethylsulfone,
5-Chloraniline-2-β-chloroethylsulfone, 5-sulfoaniline-2-β-chloroethylsulfone. In addition, in the above general formula (), when D is a β-naphthylene group, substituents include C ₁ to C ₄ alkyl groups, C ₁ to _{C 4} alkoxy groups, nitro groups, halogens, sulfonic acid groups, carboxylic acid groups. Examples include groups. When the substituent is a sulfonic acid group or a carboxylic acid group, the substitution position is α of the β-naphthylene group.
It is other than rank. Examples of these aromatic amines include the following. 2-Aminonaphthalene-4-β-sulfatoethylsulfone 2-aminonaphthalene-5-β-sulfatoethylsulfone 2-aminonaphthalene-6-β-sulfatoethylsulfone 2-aminonaphthalene-7-β -Sulfatoethylsulfone 2-aminonaphthalene-8-β-sulfatoethylsulfone 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid 2-aminonaphthalene-6-β-sulfone Artethylsulfone-8-sulfonic acid 2-aminonaphthalene-8-β-phosphatoethylsulfone-6-sulfonic acid 2-aminonaphthalene-8-vinylsulfone-
6-sulfonic acid The aromatic amine represented by the general formula () is
Examples include: 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-1,6- or -1,7-disulfonic acid Depending on the reaction conditions, the above starting compounds can be They are present or used in the form of salts, especially alkali metal salts. Further, the salt of H acid may be any salt, but from an industrial point of view, it includes alkali metal salts, alkaline earth metal salts, and amine salts, and is usually a sodium salt. The method of the present invention is carried out as follows using the above starting materials. Approximately equal moles of aromatic amines represented by general formulas () and () are mixed and diazotized. Any known diazotization method can be used.
For example, there is a method in which a predetermined amount of sodium nitrite is mixed with a mixed and dissolved solution of aromatic amines, and the mixture is injected into mineral acid. H acid or its salt in an equimolar amount to the diazo compound, or the number of moles adjusted depending on the situation, is mixed with the diazo liquid in solid, slurry or dissolved form. The mixing may be carried out by adding the diazo liquid to the coupler or vice versa. As the easiest method, H
A method of adding a neutralized acid solution to the diazo liquid is mentioned. The atmosphere in which the coupling is performed is 2 H acid.
Conditions that selectively occur in the position, that is, relatively strong acidity are required, and the preferred PH value may be changed as appropriate depending on the reactivity of the diazo compound derived from the aromatic amine represented by the general formula (). is 3 or less,
In particular, it is between 0.5 and 2. The amount of acid or pH can be adjusted by adding acid or alkali as appropriate. In this case, the temperature is preferably 40°C or less, particularly -5 to 15°C, as long as deactivation of the diazo compound does not become a problem. The incubation time is usually sufficient within 10 hours until H acid and its salts are no longer detected, but it can be changed as appropriate depending on the coupling ability of the diazo compound derived from the aromatic amine represented by the general formula (). When H acid is no longer detected, add acid binder,
Raise the pH. Any acid binder may be used as long as the addition of the acid binder does not change the fiber-reactive group, that is, the above-mentioned compound having Q and the diazo compound. Particularly safe examples include sodium carbonate and sodium hydrogen carbonate. Something like this can be mentioned. The lower limit of the pH value to be increased is the pH value at which the diazo compound remaining in the system can be coupled, and changes in compounds with group Q (including those produced at this stage) and the diazo compound to be coupled are the problem. It is assumed that the PH value is within the range where the upper limit is the PH value. This region can vary depending on the temperature, with lower temperatures leading to higher PH ranges, and conversely higher temperatures leading to lower PH ranges. A safe range is -5 to 20°C and a pH of 3 to 9, but there is no limit to these ranges depending on the properties of the final product and intermediate product. The desired product can be produced by continuing the reaction until the monoazo compound or diazo compound coupled to the 2-position of the H acid is reduced to an acceptable level in the system. It is also possible to add substances that help maintain and improve quality and yield during the diazotization and coupling steps. Additives that provide such effects include various surfactants, hydrating agents such as urea, thiourea, and ethylene glycol, coupling catalysts such as sodium formate and sodium acetate, and protection of fiber reactive groups. Stabilizers such as known PH buffers can be added. In the method of the present invention described above, the general formula ()
Although one kind of aromatic amine selected from () and () may be used, two or more kinds selected from at least one of the aromatic amines can be used at the same time to produce a bisazo-reactive dye for which the purpose is a composition of two or more kinds of dyes. It can also be obtained in the form of The bisazo-reactive dyes or compositions thereof produced according to the present invention can optionally be demineralized by removing inorganic salts separately without cooling or by using a polymer membrane, and can be further stabilized if desired. A liquid product can be obtained by adding a dye agent or a dyeability improving agent. Alternatively, the liquid product or reaction solution can also be obtained as a powder product by evaporation, for example by spray drying. Alternatively, through salting out separation using an electrolyte such as sodium chloride or potassium chloride by a generally known method,
It may be a liquid product or a powder product. The bisazo-reactive dyes or compositions thereof according to the invention can be used for dyeing nitrogen-containing fibers, such as wool, silk, leather and polyamide fibers, and in particular cellulose-containing materials, primarily cellulosic fiber materials. For example, natural or regenerated cellulose, such as cotton or viscose rayon materials, can be dyed according to customary methods carried out using water-soluble reactive dyes. For example, in the case of cellulosic fibers, dyeing is carried out using the dyes according to the invention and acid binders such as caustic soda, sodium carbonate, phosphates, silicates or baking soda. The dyeing method can be selected depending on the nature and physical properties of the fibers, and can be, for example, exhaustion, printing, or continuous dyeing, including cold patch batch up. When dyeing with the bisazo reactive dye of the present invention or its composition, it can be dyed with a high exhaustion rate and fixation rate even though it has only one fiber-reactive group in one molecule, resulting in navy color or dyeing. A deep black dyed product is obtained. Particularly in the dyeing of cellulose fiber materials, it is excellent in that it significantly improves color variation and build-up properties, and the resulting dyed products exhibit high fastness in terms of chlorine resistance, light resistance, etc. The advantage of the method of the present invention is that the series of operations required for diazotization, which conventionally required two times, can be completed in one time, and the PH can be changed during mixing with H acid or its salt and thereafter. It is extremely advantageous in terms of reaction base placement, reaction operation, and reaction control, and the resulting dye or composition thereof is extremely excellent in various properties. Next, the present invention will be explained in more detail with reference to Examples. In the text, parts represent parts by weight. Example 1 5.63 parts of 1-aminobenzene-3-β-sulfatoethylsulfone and 2-naphthylamine-1,
Add 6.07 parts of 5-disulfonic acid to 50 parts of water, and neutralize and dissolve using a 15% aqueous sodium carbonate solution. 35%
After mixing 8.2 parts of sodium nitrite aqueous solution, this was stirred into a mixture of 9.6 parts of hydrochloric acid and about 50 parts of water.
Inject over 30 minutes and keep cool for 1 hour at 0-5°C in the presence of nitrous acid. After eliminating excess sodium nitrite with sulfamic acid, 6.19 parts of H acid was added to 20 parts of water, neutralized and dissolved with caustic soda, and the solution was injected over 1.5 hours. During this period, the pH was 0 to 1 and the temperature was 0 to 5°C. PH using 15% sodium carbonate aqueous solution
The mixture was kept cool for 1.5 hours while adjusting the pH to 1.2±0.1, and when H acid was no longer detected, the pH was increased and the mixture was stirred at 0 to 5°C for 2.5 hours at a pH of 5 to 6. By evaporating and drying the reaction solution whose pH was adjusted to 5.0 at 50-60℃,
The following structural formula (1) in free acid form: The dye represented by was obtained with a yield of 89.3%. Comparative Example 1 5.63 parts of 1-aminobenzene-3-β-sulfatoethylsulfone, 1.5 parts of 2-naphthylamine
- 6.07 parts of each disulfonic acid are diazotized separately, and 6.32 parts of the neutralized H acid are sequentially coupled by a known method to form the above dye (1).
was obtained with a yield of 90.8%. Reference Example Each of the dyes obtained in Example 1 and Comparative Example 1 was used to dye cellulose fibers in navy color.
(Dyeing conditions: unsilled cotton knit, 3% owf, 60℃,
1 hour, anhydrous mirabilite 50g/, sodium carbonate
20g/, bath ratio 1:20) As a result, similar dyeing performance was shown. Example 2 5.63 parts of 1-aminobenzene-4-β-sulfatoethylsulfone and 2-naphthylamine-1-
4.47 parts of sulfonic acid was added to 70 parts of water and dissolved in the same manner as in Example 1 to perform diazotization. Add 6.19 parts of H acid to 20 parts of water and neutralize and dissolve with caustic soda.
The injection took place over 1.5 hours. During that time, the pH was between 0 and 1. The temperature was 0-5°C. Adjust the pH to 2 ± 0.5 using 15% sodium carbonate and keep it cool for 1.5 hours. After confirming the disappearance of H acid, add 1.5 parts of sodium formate, gradually raise the pH, and keep at 0-5℃ for 4 hours at 7.0-8.5. It was stirred with The reaction solution whose pH was adjusted to 5.0 was heated to 50-60
By evaporating to dryness at °C, the following structural formula (2) is obtained in the free acid form: The dye represented by was obtained with a yield of 88.0%, which showed a yield and quality comparable to those of known methods. Example 3 Add 1 to a slurry solution with a pH of 2 to 2.5 containing 6.19 parts of H acid.
Add a diazotization solution consisting of 5.63 parts of -aminobenzene-3-β-sulfatoethylsulfone and 6.07 parts of 2-naphthylamine 1,5-disulfonic acid,
Stir at ~5°C and pH 1-2. If H acid is no longer detected, increase the pH and increase the pH at 5 to 10°C.
Stir for hours. Potassium chloride was added in an amount equivalent to 20% of the liquid volume, salted out, and filtered to obtain the dye (1) above in the form of potassium salt. Examples 4-29 Useful bisazo-reactive dyes were obtained by applying the method of the present invention using the following aromatic amines. The first column of the method below shows the aromatic amine represented by the general formula (), the second column shows the aromatic amine represented by the general formula (), and the third column shows the color tone of the bisazo reactive dye on cellulose fiber. shows.

【table】

【table】

【table】

[Table] Comparative Example 2 An aromatic amine represented by the general formula () and the following structurally similar compound in place of the aromatic amine represented by the general formula () 1-aminobenzene-2-sulfonic acid 1-amino benzene-3-sulfonic acid 1-aminobenzene-4-sulfonic acid 1-aminobenzene-2,5-disulfonic acid 2-naphthylamine-3,6-disulfonic acid 2-naphthylamine-6-sulfonic acid When the method of the present invention was applied to the mixture, dyes were obtained which were inferior in yield and quality compared to dyes obtained by known methods. Example 30 5.63 parts of 1-aminobenzene-3-β-sulfatoethylsulfone and 2-naphthylamine-1,
After mixing, neutralizing and dissolving 3.04 parts of 5-disulfonic acid and 2.24 parts of 2-naphthylamine-1-sulfonic acid, diazotization is carried out according to Example 1 or 2. H
A neutralized solution containing 6.19 parts of acid was added dropwise over 2 hours, and the pH was 0 to 1 and the temperature was 0 to 5°C. Then PH1.5~2.0
Keep for 1 hour, add 1.5 parts of sodium formate, and gradually
The pH was raised to 0-5°C, and the mixture was stirred for 4 hours at PH7.0-8.5, 3 parts of sodium monophosphate was added, the pH was adjusted to 5.0±0.2, and the mixture was evaporated to dryness at 50-60°C. Examples 1 and 4 A composition containing approximately equimolar amounts of bisazo dye was obtained. Example 31 2.82 parts of 1-aminobenzene-4-β-sulfatoethylsulfone and 1-aminobenzene-3-
2.82 parts of β-sulfatoethyl sulfone and 2-
Mix 4.47 parts of naphthylamine-1-sulfonic acid;
After neutralization and dissolution, the composition was produced in the same manner as in Example 30 to obtain a composition containing approximately equal moles of the bisazo dyes of Examples 2 and 4. Example 32 In Example 31, 1-aminobenzene-3-β
- A composition containing approximately equimolar moles of the bisazo reactive dyes of Examples 2 and 5, except that 1-aminobenzene-2-β-sulfatoethylsulfone was used instead of sulfatoethylsulfone. I got something. Example 33 A 3:7 mixture of 1-aminobenzene-3 and 4-β-sulfatoethylsulfone and a 5:5 molar ratio of 2-naphthylamine-1-mono and -2,5-disulfonic acid. Using the mixture, a four-component bisazo reactive dye composition was prepared in the same manner as described above. Reference Example Cellulose fibers were dyed using the reactive dyes obtained in Examples 2 to 33 or their compositions, and various fastness values,
In particular, a deep navy dyed product was obtained which showed excellent chlorine fastness and good dyeing efficiency.

Claims (1)

[Claims] 1 In the form of a free acid, the following general formula () [In the formula, D may have one or two substituents selected from a _C1 to _C4 alkyl group, a _C1 to _C4 alkoxy group, a nitro group, a halogen, and a sulfonic acid group. represents a good phenylene group or an optionally substituted β-naphthylene group, and Q is -
SO ₂ CH=CH ₂ or −SO ₂ CH ₂ CH ₂ R (here R
represents a group that is eliminated by the action of an alkali), and X represents a hydrogen atom or a sulfonic acid group. ] In producing the bisazo reactive dye shown in
The following general formula () Q-D-NH ₂ () [wherein D and Q have the above-mentioned meanings. ] Aromatic amines represented by and the following general formula () [In the formula, X has the above meaning. ] A diazo compound in which multiple types coexist obtained by mixing and simultaneously diazotizing 2-naphthylamine-1-sulfonic acids represented by the above, and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid or a salt thereof. A method for producing a bisazo-reactive dye represented by the general formula (), which comprises coupling.