JPS5944327B2 - Liquid dye preparations of reactive dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid aqueous dye preparation containing a specific dye and a dyeing and printing method using the same.

That is, the present invention provides a reactive dye corresponding to the following formula (1) in the form of a free acid [(1), (), (), (), (V) or ()]
The present invention relates to a liquid aqueous dyeing preparation containing one of the following.

This dyeing preparation contains one of the dyes mentioned above, in particular as its alkali salt, especially sodium salt, of the formula (), (), (), (
), (V) or () 5 to 35% by weight with respect to pure dyes
in particular as an aqueous solution in a concentration of 15 to 30% by weight,
and the pH value is from 3 to 7, preferably from 5.5 to 6.8, in addition to sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium borate, acidic sodium or -potassium salts of phosphoric acid and and/or a mixture of various sodium or potassium salts of phosphoric acid in an amount of 1 to 5% by weight.

The dye of the formula () is described in the West German Patent Specification (hereinafter DT-PS
1206107 (abbreviated as ), the dye of formula () is from Example 1 of DT-PS No. 1282213, the dye of formula () is from Example 1 of DT-PS No. 1150163, and the dye of formula () is from Example 1 of DT-PS No. 1150163 ) dyes are described in the West German Patent Publication (hereinafter D
From Example 8 of No. 1619491 (abbreviated as T-AS), the dye of formula (V) is
From Table Example 1 on page 24 of No. 1544538 (abbreviated as T-0S), the dye of formula () is DT-0S No. 180452.
No. 4, Examples 4 and 5.

After synthesis, water-soluble reactive dyes are isolated by salting out the dye from the aqueous reaction solution by a conventional method, collecting the precipitated salt dye mixture by suction, and drying the resulting pressed cake. do.

Another industrially customary method for isolating dissolved, generally water-soluble dyes from their synthesis solutions is direct drying, for example spray drying of the preparation solutions. For the desired dyeing application, the salt-containing dye powder is generally adjusted to the specific dye content by addition of a neutral inorganic salt, for example sodium sulfate, even after its drying.

However, this customary unpowdered form of reactive dyestuffs is difficult to operate with, for example when filling or refilling, weighing or placing, or when using dye liquors or printing pastes.
When preparing dyestuffs, there are several disadvantages which arise, in particular, from the dust generation of such powdered dyeing preparations.

In this case, this dust generation not only causes annoyance to workers in production or usage operations, but also
or in the printing factory, sedimentation of the dye powder may result in undyed or already dyed products being dyed with unpleasant stains. On the other hand, whenever powdered dyestuffs are dust-proofed using customary dust-proofing agents based on mineral oil, there is always a risk that oily deposits will form during dyeing and printing. This results in smeared and therefore useless dyeings and prints. Furthermore, with such powdered dyestuffs, it is often not possible to carry out industrially intended rational operations, such as continuous dyeing processes or automatic metering and weighing. These drawbacks, which can also be said for the powdered dyes of formulas (1), (), (), (), (V) and () mentioned above, can be overcome by the liquid dye preparation according to the invention of the respective dyes. Completely avoided.

Furthermore, the new preparations offer advantages over powdered dye preparations, both for the dye manufacturer and for the dye user, in that the salt load of the waste water is significantly reduced. That is, novel liquid dyeing preparations of dyes of formula (1), (), (), (), () or () can be prepared by directly using the clarified dye solution obtained during the synthesis according to the present invention. , if desired, preferably by concentration, e.g. by distilling off a portion of the water under vacuum, or alternatively preferably by drying, e.g. spray-drying, the same dye solution obtained and clarified during the synthesis. is added to adjust the desired relatively high dye content.

In all cases, a buffer is also added to the dye solution. In order to produce dyeing preparations according to the invention containing up to 35% by weight of dyestuff, the content of inert salts, such as sodium sulfate or sodium chloride, in the clarified aqueous dyestuff solution should be as low as possible and the synthetic It is advantageous to start from aqueous dye solutions which are less than 50% by weight of the dye content of these dye solutions obtained in the process.

When producing dyeing preparations with relatively low dye contents, for example up to 15% by weight dye content, the inert salt content of the starting solution should be less than its dye content. Does the dye aqueous solution obtained during synthesis generally contain inert salts? ?
・It is within the limit of x. Solutions of reactive dyestuffs containing β-sulfatoethylsulfonyl groups obtained by esterification of β-hydroxyethylsulfonyl groups with concentrated sulfuric acid also require the addition of sulfuric acid and The excess of sulfuric acid required to form the ester groups cannot be neutralized with caustic soda solution or other agents that yield readily soluble inert salts. In this case, it is preferable to neutralize the excess sulfuric acid with calcium carbonate and to separate the dye solution from the sparingly soluble calcium sulfate by filtering. This method is particularly applicable to Example 1 of DT-0S No. 1955849, DTOS No. 2
Example 1 of No. 049664 and DT-0S No. 2060081
Example 2 of the issue. The formula obtained during synthesis (
1), (), (), (), (), (V) or () dye solution contains 5-15% by weight of dye and water is distilled off by adding dry dye or under vacuum. By doing so, a dye content of about 30-35% by weight can be achieved. This means that the dye manufacturer does not have to deal with mother liquors which have a very high salt content and are partially saturated with salt, and the dye user also has a significant reduction in the salt content of the waste water.

This is because the amount of salt used for preparing the dye powder can be dispensed with when producing the liquid preparation according to the invention. The buffering agents used in the dyeing preparations according to the invention are suitable, in particular, for reducing the dye yield without causing chemical reactions with the β-sulfatoethylsulfonyl group or its vinylsulfonyl homologs and thereby increasing the dye yield. Any buffering agent that does not reduce the /)′
-X substances include, for example, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, acidic sodium salts and acidic potassium salts of phosphoric acid, mixtures of various sodium or potassium salts of phosphoric acid, and sodium borate. Particularly advantageous among these are sodium borate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
The reaction mechanism between reactive dyes of the type described above and cellulose fibers is generally known. After the β-sulfatoethylsulfonyl group is converted into a vinylsulfone group in the presence of an alkaline agent by reaction (1) in the reaction scheme below,
Reaction (4) results in the formation of covalent bonds between the fiber substrate and the dye molecules, resulting in the well-known good fastness properties of dyeings with reactive dyes. Furthermore, since the use of reactive dyes having a β-sulfatoethylsulfonyl group, this reactive group, in its vinylsulfonyl form, has a high resistance not only in the presence of alkalis but also in acidic regions. Also in the diagram (
It is known that according to 2) or (3), a competitive reaction with respect to the original dyeing reaction (4) occurs, and the reaction with water results in a β-hydroxyethylsulfonyl group having poor reactivity with the fiber matrix.

Reaction scheme: (In the formula, F means the residue of the dye molecule, Cell.OH
means cellulose.

) Hydrolysis (2) and addition of water (3) are practically not reversible under the dyeing conditions and therefore reduce the dyeing rate.

For this reason, in the production of water-soluble reactive dyes, the separation and drying of the reactive dye from the synthetic solution as mentioned above should be carried out immediately after the synthesis, and the loss of dye density due to the above-mentioned reasons should be avoided. Do this in a way that avoids.

Therefore reactive dyes (1), (), (), (), (V)
It was all the more surprising to find that a neutral to weakly acidic buffered aqueous solution containing one of the following:

Aqueous solutions of dyes of formula (1), (), (), (), (V) or () according to the invention may be stored at room temperature for several months, for example 6 months, or at 50° C. for several weeks, for example 8 weeks. Produces five colors of dyeing and printing with constant dyeing density even during storage.

The dyeing preparations according to the invention are prepared in the generally known manner customary for reactive dyes, after dilution with water and optionally with the addition of customary dyeing auxiliaries or, correspondingly, with the pastes customary in the printing industry. dyeing and printing of fiber materials consisting of wool, silk, polyamide and natural or regenerated cellulose, or fiber mixtures containing one or more of the types of fibers mentioned, after addition of agents and optionally printing aids; suitable for

Therefore, the dyeing preparation according to the present invention containing specific dyes among the dyes used according to the original invention has extremely excellent effects.

The following examples are intended to illustrate the invention.

EXAMPLE 1 A clarified aqueous dye solution of a dye of the following formula (known from Table Example 1 on page 24 of DT-0S No. 1544538) with a pH value of 5.8 and a dye content of 15% by weight. A dye obtained by spray-drying another part of the same clarified dye solution to -150 parts by weight of -150 parts by weight obtained by diazotizing, coupling and further complexing the corresponding starting compounds during synthesis in a conventional manner. 36 parts by weight of dry dye powder having a content of 70% by weight are added with stirring.

The 186 parts by weight of the aqueous solution thus obtained containing 25.7% by weight of pure dye was, after addition of 5 parts by weight of disodium hydrogen phosphate, 191 parts by weight of an aqueous dye preparation having a pure dye content of 25% by weight and a pH value of 642. occurred. Using 2 parts by weight of this solution, a dye bath, a padding solution and a printing paste are prepared by a known conventional method, and then the dye bath is prepared by a dyeing process. When applied and fixed on cotton in the manner customary for reactive dyes, a dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of an unadjusted powder containing 50% by weight of pure dyestuff is correspondingly used. Black or gray dyeings and prints were obtained with exactly the same color intensity as those produced using the method.

This color intensity of the dyeings and prints was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 2 A clear aqueous dye solution of the dye mentioned in Example 1, with a pH value of 5.7 and a dye content of about 11% by weight.
48 parts by weight of a dry dye powder with a dye content of 60% by weight, obtained by spray-drying another part of the same clear dye solution, was added to -200 parts by weight of the resultant coupling and complexing with stirring. Ta.

The thus obtained 248 parts by weight of an aqueous solution containing 20.5% by weight of the pure dye was mixed with 6 parts by weight of disodium hydrogen phosphate to form an aqueous dyeing preparation 254 having a pure dye content of 20% by weight and a pH value of 6.0. Yields parts by weight. Using 5 parts by weight of this solution, dyebaths, padding liquids and printing pastes are prepared by known conventional methods, which, when applied and fixed on cotton in a manner customary for reactive dyes, contain 50% by weight of pure dyestuff. black or gray dyeings and prints having exactly the same color strength as those produced using corresponding dye baths, badging liquids or printing pastes of the same concentration containing 2 parts by weight of unadjusted powder are obtained. Ta.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 3 The pH value is 5.8 and the dye content is 15% by weight.
A clear aqueous dye solution of the dye mentioned in Example 1, obtained by diazotization, coupling and complexation of the corresponding starting compounds in the customary manner for the synthesis of dyes.
To 150 parts by weight, 5 parts by weight of hydrogen phosphate hydroxide was added.

From this dye solution, 65 parts by weight of water is distilled off at 60° C. under a vacuum of 18 mmHg while stirring. There was thus obtained 90 parts by weight of an aqueous dye preparation with a pure dye content of 25% by weight and a pH value of 6.4 at 20°C. Using 2 parts by weight of this solution, dyebaths, padding liquids and printing pastes are prepared by known conventional methods, which, when applied and fixed on cotton in a manner customary for reactive dyes, contain 50% by weight of pure dyestuff. black or gray dyeings and prints having exactly the same color strength as those produced using corresponding dye baths, padding liquids or printing pastes of the same concentration containing 1 part by weight of unadjusted powder are obtained. Ta.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 4 The pH value is 5.7 and the dye content is 11% by weight.
A clear aqueous dye solution of the dye mentioned in Example 1, obtained by diazotization, coupling and complexation of the corresponding starting compounds in the customary manner in the synthesis of dyes.
To 200 parts by weight, 48 parts by weight of a dry dye powder having a dye content of 60% by weight, obtained by spray-drying another portion of the same clear dye solution, was added with stirring.

248 parts by weight of the aqueous solution containing 20.5% by weight of pure dye thus obtained, after addition of 6 parts by weight of sodium borate, yields 254 parts by weight of an aqueous dyeing preparation having a pure dye content of 20% by weight and a pH value of 5.9. occurred. Using 5 parts by weight of this solution, a dyebath, a padding liquid and a printing paste are prepared by a known conventional method, and when applied and fixed on cotton in a manner customary for reactive dyes, 50% by weight of pure dyestuff is obtained. black or gray dyeings and prints having exactly the same color strength as those produced using corresponding dye baths, padding liquids or printing pastes of the same concentration containing 2 parts by weight of unadjusted powder was gotten.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 5 The pH value is 6.0 and the dye content is 15% by weight.
A clear aqueous dye solution of a dye of the formula (known from DT-AS 1619491, Example 8), which is prepared by diazotization and coupling of the corresponding starting compound in the customary manner in the synthesis of the dye. 37 parts by weight of a dry dye powder having a dye content of 67% by weight, obtained by spray-drying another portion of the same clear dye solution, are added to -200 parts by weight obtained while stirring.

The thus obtained 237 parts by weight aqueous solution containing 23.1% by weight of pure dye and having a pH of 6.0 had a pure dye content of 22.5% by weight, P after addition of 6 parts by weight of disodium hydrogen phosphate.
This resulted in an aqueous dyeing preparation with an H value of 6.2. Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A black or gray color having exactly the same strength of color as produced using a corresponding dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 45% by weight of dyestuff. A dyeing and a print were obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 6 A clear aqueous dye solution of the dye mentioned in Example 5 with a pH value of 5.5 and a dye content of about 14.5% by weight, which is prepared by diazotizing the corresponding starting compound in the customary manner in the synthesis of the dye. and −20 obtained by coupling
Dry dye powder 45 with a dye content of 64% by weight obtained by spray-drying 0 part by weight of another part of the same clear dye solution
Parts by weight were added with stirring.

245 parts by weight of the aqueous solution containing 23.6% by weight of pure dye obtained in this way has a pure dye content of 22.5% by weight and a pH value of 63 after addition of 12 parts by weight of disodium hydrogen phosphate.
This yielded 257 parts by weight of an aqueous dyeing preparation of No. 2. Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A black or gray color having exactly the same strength of color as produced using a corresponding dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 45% by weight of dyestuff. A dyeing and a print were obtained.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 4 months.

Example 7 A clear aqueous dye solution of the dye mentioned in Example 5, with a pH value of 5.5 and a dye content of 14.5% by weight. and −20 obtained by coupling
12 parts by weight of disodium hydrogen phosphate were added to 0 parts by weight.

From this dye solution, at 60°C and 18 mm while stirring
83 parts by weight of water were distilled off under Hg vacuum. The pure dye content is thus 22.5% by weight and the pH-value is 6.5% at 20°C.
129 parts by weight of an aqueous dye preparation of No. 5 was obtained. Using 2 parts by weight of this solution, a dyebath, a padding liquid and a printing paste are prepared in a conventional manner known and applied to cotton in a manner customary for reactive dyes and, when fixed, contain 45% by weight of pure dyestuff. Black or gray dyeings and prints with exactly the same color strength as those produced using a dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder are obtained with exactly the same color strength as those produced using the corresponding L-. It was done.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 8 The pH value is 6.0 and the dye content is 12% by weight.
A clear aqueous dye solution of the dye mentioned in Example 5 - 200 parts by weight of the same clear dye obtained by diazotizing and coupling the corresponding starting compounds in the customary manner for the synthesis of dyes. 14 parts by weight of a dry dye powder having a dye content of 67% by weight obtained by spray drying another portion of the solution was added with stirring.

The thus obtained PH- containing 15.6% by weight of pure dye
214 parts by weight of an aqueous solution with a value of 6 gave, after addition of 8 parts by weight of sodium borate, an aqueous dyeing preparation with a pure dye content of 15% by weight and a pH value of 6.2. Using 3 parts by weight of this pH stabilized solution, dye baths, padding liquids and printing pastes are prepared by known conventional methods, and when applied and fixed on cotton using methods customary for reactive dyes, pure A black or gray color having exactly the same strength of color as produced using a corresponding dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 45% by weight of dyestuff. A dyeing and a print were obtained.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 4 months.

Example 9 The pH value is 6.0 and the dye content is 15% by weight.
A clear aqueous dye solution of a dye of the following formula (known from DT-0S No. 1804524, Examples 4 and 5) is prepared by diazotizing and coupling the corresponding starting compounds in the usual manner during the synthesis of the dye. -10 obtained
Dry dye powder 24 with a dye content of 67% by weight obtained by spray-drying 0 part by weight of another part of the same clear dye solution
．． 5 parts by weight were added with stirring.

The thus obtained P containing 25.3% by weight of pure dye
124.5 parts by weight of an aqueous solution with an H-value of 6 had a pure dye content of 25% by weight after addition of 2 parts by weight of disodium hydrogen phosphate;
An aqueous dye preparation with a pH value of 6.0 was obtained. This PH
Dye baths, padding liquids and printing pastes are prepared in a known and conventional manner using 2 parts by weight of a stabilized solution of 2 parts by weight of a stabilized solution of 50% pure dye. Yellow dyeings and prints with exactly the same color intensity as those produced using corresponding dye baths, padding liquids or printing pastes of the same concentration containing 1 part by weight of unadjusted powder containing % by weight Obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 10 A clear aqueous dye solution of the dyestuff given in Example 9 with a pH value of 5.8 and a dye content of approximately 13% by weight, which is obtained by diazotizing the corresponding starting compounds in the customary manner in the synthesis of the dyestuffs. and −20 obtained by coupling
Dry dye powder 34 with a dye content of 65% by weight obtained by spray-drying 0 parts by weight of another part of the same clear dye solution
Parts by weight were added with stirring.

234 parts by weight of the aqueous solution containing 20.5% by weight of pure dyestuff obtained in this way is an aqueous dyeing having a PH-value of 6.1 with a pure dyestuff content of 20% by weight after addition of 6 parts by weight of disodium hydrogen phosphate. A preparation was produced. Using 5 parts by weight of this pH stabilized solution, a dyebath, a dye bath and a printing paste are prepared by a known conventional method, and this is applied to cotton and fixed by a method customary for reactive dyes. , a yellow color having exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 2 parts by weight of unadjusted powder containing 50% by weight of pure dyestuff. A dyeing and a print were obtained.

Z5 This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 11 A clear aqueous dye solution of the dye mentioned in Example 9 with a pH value of 6 and a dye content of 13% by weight, which is prepared by diazotizing and coupling the corresponding starting compounds in the customary manner in the synthesis of the dye. 3 parts by weight of disodium hydrogen phosphate were added to -200 parts by weight obtained by.

73 parts by weight of water is distilled off from this dye solution under a vacuum of 18 mmHg at 60° C. while stirring. 130 parts by weight of an aqueous dyeing preparation with a pure dye content of 20% by weight and a pH value of 6.1 at 20 DEG C. were thus obtained. Using 5 parts by weight of this pH stabilized solution, dye baths, padding liquids and printing pastes are prepared by known conventional methods, and when applied and fixed on cotton using methods customary for reactive dyes, pure A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 2 parts by weight of unadjusted powder containing 50% by weight of dyestuff and A print was obtained.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 12 A clear aqueous dye solution of the dye mentioned in Example 9 with a pH value of 6 and a dye content of 15% by weight, which is prepared by diazotizing and coupling the corresponding starting compounds in the customary manner in the synthesis of the dye. 27 parts by weight of a dry dye powder having a dye content of 67% by weight, obtained by spray-drying another portion of the same clear dye solution, were added to -100 parts by weight obtained by stirring with stirring.

The 127 parts by weight of the aqueous solution thus obtained containing 26.1% by weight of pure dye gave, after addition of 8 parts by weight of sodium borate, an aqueous dyeing preparation with a pure dye content of 20% by weight and a pH value of 6. . Using 2 parts by weight of this pH stabilized solution, a dye bath, a padding solution and a printing paste are prepared using a known conventional method, and this is applied to cotton using a method customary for reactive dyes and fixed. A yellow color having exactly the same intensity of color as produced by correspondingly using a dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of an unadjusted powder containing 50% by weight of pure dyestuff. dyeing and printing were obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 13 A clear aqueous dye solution of the dyestuff of formula (1) as defined above, with a pH value of 5.8 and a dye content of 15% by weight. Obtained by coupling −
To 100 parts by weight, 19 parts by weight of a dry dye powder having a dye content of 67% by weight, obtained by spray-drying another portion of the same clear dye solution, were added with stirring.

The thus obtained 119 parts by weight aqueous solution containing 23.3% by weight of pure dye and having a pH value of 5.8 has a pure dye content of 22.5% by weight of P after addition of 4 parts by weight of disodium hydrogen phosphate.
This resulted in an aqueous dyeing preparation with a H value of 6,0. Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A yellow dyeing with exactly the same strength of color as produced by correspondingly using a dyebath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 45% by weight of dyestuff and A print was obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 14 A clear aqueous dye solution of the dyestuff of formula (1) as defined above, with a pH value of 5.8 and a dye content of about 13% by weight, which is obtained by diazotizing the corresponding starting compound in the customary manner for the synthesis of the dyestuff. , and 17 parts by weight of a dry dye powder having a dye content of 65% by weight, obtained by spray-drying another part of the same clear dye solution to -100 parts by weight obtained by coupling, with stirring. added.

The thus obtained 117 parts by weight aqueous solution containing 20.5% by weight of pure dye had a pH value of 6.1 with a pure dye content of 20.0% by weight after addition of 3 parts by weight of disodium hydrogen phosphate.
This resulted in an aqueous dye preparation. Using 5 parts by weight of this pH stabilized solution, dye baths, padding liquids and printing pastes are prepared by known conventional methods, and when applied and fixed on cotton using methods customary for reactive dyes, pure Dye 50% by weight
a dyebath of the same concentration containing 2 parts by weight of unadjusted powder containing;
Yellow dyeings and prints were obtained with exactly the same color strength as those produced using the corresponding padding liquid or print paste.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 15 A clear aqueous dye solution of the dyestuff of the formula (1) described above, with a pH value of 6.0 and a dye content of 12% by weight. Obtained by coupling −
Add 3 parts by weight of disodium hydrogen phosphate to 200 parts by weight.

From this dye solution, 96.5 parts by weight of water is distilled off at 60° C. under a vacuum of 18 g Hg while stirring. 106.5 parts by weight of an aqueous dye preparation with a pure dye content of 22.5% by weight and a pH value of 6.1 at 20 DEG C. were thus obtained. Using 2 parts by weight of this solution, a dyebath, a padding liquid and a printing paste are prepared in a conventional manner known and applied to cotton in a manner customary for reactive dyes and, when fixed, contain 45% by weight of pure dyestuff. Yellow dyeings and prints were obtained which had exactly the same color strength as those produced using the corresponding dye baths, padding liquors or printing pastes of the same concentration containing 1 part by weight of unadjusted powder. This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 16 A clear aqueous dye solution of the dyestuff of formula (1) as described above, with a pH value of 6.0 and a dye content of 13% by weight. -1 obtained by coupling
Dry dye powder 2 with a dye content of 65% by weight obtained by spray-drying 00 parts by weight of another part of the same clear dye solution
5 parts by weight were added with stirring.

125 parts by weight of the thus obtained aqueous solution containing 23.4% by weight of the pure dye was added with 5 parts by weight of sodium borate to form an aqueous dyeing preparation having a pure dye content of 22.5% by weight and a pH value of 6.0. occured. Zυ Using 2 parts by weight of this PH stabilized solution, a dye bath, padding solution and printing paste are prepared by a known conventional method, and when this is applied to cotton and fixed by a method customary for reactive dyes, A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadulterated powder containing 45% by weight of pure dyestuff. and a print was obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 17 A clear aqueous dye solution of the dyestuff of the formula () above, with a pH value of 6.0 and a dye content of 13% by weight, which is prepared by diazotizing the corresponding starting compound in the customary manner in the synthesis of the dyestuff and To -100 parts by weight obtained by coupling, 12 parts by weight of a dry dye powder with a dye content of 60% by weight, obtained by spray-drying another part of the same clear dye solution, was added with stirring. Ta.

The thus obtained product contained 18% by weight of pure dye and had a pH value of 6.
. 112 parts by weight of an aqueous solution with a pure dye content of 17.5% by weight after addition of 4 parts by weight of disodium hydrogen phosphate
This resulted in an aqueous dye preparation with a value of 6.3.

Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 35% by weight of dyestuff and A print was obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

Example 18 A clear aqueous dye solution of the dyestuff of the formula () above, with a pH value of 5.8 and a dye content of approximately 13% by weight, which is prepared by diazotizing the corresponding starting compound in the customary manner in the synthesis of dyestuffs. and obtained by coupling −
To 200 parts by weight, 44 parts by weight Z7 parts by weight of a dry dye powder having a dye content of 54% by weight, obtained by spray-drying another part of the same clear dye solution, were added with stirring.

244 parts by weight of the aqueous solution containing 20.4% by weight of pure dye obtained in this way was subjected to an aqueous dyeing preparation with a pure dye content of 20.0% by weight and a pH value of 6.1 after addition of 5 parts by weight of disodium hydrogen phosphate. produced something. Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 40% by weight of dyestuff and A print was obtained.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 19 A clear aqueous dye solution of the dyestuff of the formula () above, with a pH value of 6.0 and a dye content of 15% by weight, which is prepared by diazotizing the corresponding starting compound in the customary manner in the synthesis of dyestuffs, and -2 obtained by coupling
Add 5 parts by weight of disodium hydrogen phosphate to 00 parts by weight.

From this dye solution, 18ml/LHg at 60℃ while stirring.
55 parts by weight of water are distilled off under vacuum. 150 parts by weight of an aqueous dyeing preparation with a pure dye content of 20% by weight and a pH value of 6.3 at 20 DEG C. were thus obtained. Using 2 parts by weight of this solution, a dyebath, a padding liquid and a printing paste are prepared in a conventional manner known and applied to cotton in a manner customary for reactive dyes and, when fixed, contain 40% by weight of pure dyestuff. Yellow dyeings and prints were obtained which had exactly the same color strength as those produced using the corresponding dye baths, padding liquors or printing pastes of the same concentration containing 1 part by weight of unadjusted powder.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 20 A clear aqueous dye solution of the dyestuff of the above formula () with a pH value of 6.0 and a dye content of 15% by weight. -1 obtained by
Dry dye powder 1 with a dye content of 60% by weight obtained by spray-drying 00 parts by weight of another part of the same clear dye solution
5 parts by weight were added with stirring.

115 parts by weight of the aqueous solution thus obtained containing 20.8% by weight of pure dye yielded, after addition of 5 parts by weight of sodium borate, an aqueous dyeing preparation having a pure dye content of 20% by weight and a pH value of 6.0. Ta. Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 40% by weight of dyestuff and A print was obtained.

The color depth of printing and dyeing remained unchanged even when the freshly prepared aqueous preparation described above was stored at 50° C. in a closed container for 6 weeks.

Example 21 A clear aqueous dye solution of the dyestuff of the formula () above, with a pH value of 5.7 and a dye content of 12% by weight, which is prepared by diazotizing the corresponding starting compound in the customary manner in the synthesis of dyestuffs, and 1 obtained by coupling
Dry dye powder 2 with a dye content of 70% by weight obtained by spray-drying 00 parts by weight of another part of the same clear dye solution
4.5 parts by weight was added with stirring.

124.5 parts by weight of the thus obtained aqueous solution containing 23.4% by weight of pure dye and having a pH value of 5.7 had a pure dye content of 22.5% by weight and a pH of 5.7 after adding 5 parts by weight of disodium hydrogen phosphate. This resulted in an aqueous dyeing preparation with a value of 6.0. Using 2 parts by weight of this pH stabilized solution, a dyebath, a padding solution and a printing paste are prepared in a known conventional manner, and when applied and fixed on cotton in a manner customary for reactive dyes, a pure A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same strength containing 1 part by weight of unadjusted powder containing 45% by weight of dyestuff. and a print was obtained.

The color depth of printing and dyeing remained unchanged even when the above-mentioned new aqueous preparation was stored in a closed container at 50° C. for 6 weeks.

Example 22 A clear aqueous dye solution of the dyestuff of the above formula () with a pH value of 5.8 and a dye content of about 13% by weight, which is obtained by diazotizing the corresponding starting compound in the customary manner in the synthesis of dyestuffs. and obtained by coupling −
To 200 parts by weight, 34 parts by weight of a dry dye powder having a dye content of 64% by weight, obtained by spray drying another portion of the same clear dye solution, were added with stirring.

The thus obtained 234 parts by weight aqueous solution containing 20.4% by weight of pure dyestuff, after addition of 5 parts by weight of disodium hydrogen phosphate, has an aqueous dyeing preparation with a pure dyestuff content of 20.0% by weight and a pH-value of 6.1. produced something. Using 5 parts by weight of this pH stabilized solution, dye baths, padding liquids and printing pastes are prepared by known conventional methods, and when applied and fixed on cotton using methods customary for reactive dyes, pure A yellow dyeing with exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same strength containing 2 parts by weight of unadjusted powder containing 50% by weight of dyestuff. and a print was obtained.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 23 A clear aqueous dye solution of the dyestuff of the formula () above, with a pH value of 6.0 and a dye content of 13% by weight, which is prepared by diazotizing the corresponding starting compound in the customary manner in the synthesis of dyestuffs and 5 parts by weight of disodium hydrogen phosphate are added to -200 parts by weight obtained by coupling.

87.5 parts by weight of water is distilled off from this dye solution under a vacuum of 18 mmHg at 60° C. while stirring. 115.5 parts by weight of an aqueous dye preparation with a pure dye content of 22.5% by weight and a pH value of 6.1 at 20 DEG C. were thus obtained. Using 2 parts by weight of this solution, a dyebath, a padding liquid and a printing paste are prepared in a conventional manner known and applied to cotton in a manner customary for reactive dyes and, when fixed, contain 45% by weight of pure dyestuff. Yellow dyeings and prints were obtained which had exactly the same color strength as those produced using the corresponding dye baths, padding liquors or printing pastes of the same concentration containing 1 part by weight of unadjusted powder.

This color strength of the prints and dyeings remained unchanged even when the new aqueous preparation described above was stored in a closed container at 20° C. for 3 months.

Example 24 A clear aqueous dye solution of the dyestuff of the formula () above, with a pH value of 6.0 and a dye content of 12% by weight. To -100 parts by weight obtained by coupling, 25 parts by weight of dry dye powder with a dye content of 70% by weight, obtained by spray-drying another part of the same clear dye solution, was added with stirring. .

125 parts by weight of the thus obtained aqueous solution containing 23.9% by weight of the pure dye was added with 6 parts by weight of sodium borate to form an aqueous dyeing preparation having a pure dye content of 22.5% by weight and a pH value of 6.0. occured. Using 2 parts by weight of this pH stabilized solution, a dye bath, a padding solution and a printing paste are prepared by a known conventional method, and this is applied to cotton and fixed by a method customary for reactive dyes. , a yellow color having exactly the same strength of color as produced using a corresponding dye bath, padding liquid or printing paste of the same concentration containing 1 part by weight of unadjusted powder containing 45% by weight of pure dyestuff. A dyeing and a print were obtained.

This color intensity of printing and dyeing was maintained even when the new aqueous preparation described above was stored in a closed container at 50°C for 6 weeks.
Obtained without change.

The present invention has been described in detail above, and specific aspects thereof and related objects will be listed below.

(1) Staining preparation according to the claims comprising one or more buffering agents from the system of sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium acid phosphate, potassium acid phosphate and sodium borate. thing.

(2) A dyeing preparation according to the claims, which contains sodium borate.

(3) The dye preparation according to the claims, which comprises sodium dihydrogen phosphate and (or) disodium hydrogen phosphate.

(4) Dyeing or printing using one of the dyeing preparations described in the claims and the above item (g) (3);
Fiber materials consisting of wool, silk, polyamide and natural or regenerated cellulose or fiber mixtures containing one or more of the above-mentioned types of fibers.

Claims (1)

[Claims] In the form of a free acid, the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) or the following formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) or the following formula (I
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) or the following formula (
IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) or the following formula (V
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) or the following formula (V
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Dye corresponding to (VI) (I), (II), (III), (IV), (V) or (V
5 to 35% by weight of I) and sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium borate,
Acidic sodium or -potassium salts of phosphoric acid and/or mixtures of various sodium or potassium salts of phosphoric acid 1 to 5
% by weight and a pH value of 3 to 7. In the form of free acid, the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) or the following formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) or the following formula (I
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) or the following formula (
IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) or the following formula (V
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) or the following formula (V
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Dyes corresponding to (I), (II), (III), (IV), (
V) or 5 to 35% by weight of (VI) and sodium acetate,
containing 1 to 5% by weight of potassium acetate, sodium oxalate, potassium oxalate, sodium borate, acidic sodium or -potassium salts of phosphoric acid and/or mixtures of various sodium or potassium salts of phosphoric acid and having a pH value of 3. Textile materials consisting of wool, silk, polyamide or natural or regenerated cellulose or containing one or more of the above-mentioned types of fibers, characterized by the use of liquid aqueous dyeing preparations of reactive dyes of ~7 A method of dyeing or printing a fiber mixture.