DE102008026403A1 - Dyeing cellulose fibres, e.g. cotton fabric, with reactive vinylsulfone dyes, involves adding dye-bath components in a special sequence to optimise the relation between physical adsorption and chemical reactivity - Google Patents

Abstract

A method (M1) for dyeing cellulose fibres with reactive dyes of the vinylsulfone type, involves adding the (optional) auxiliary substance to the textile material in the dye bath before adding the alkali fixer, then adding the dyestuff followed by a buffer for pH 7-10 and then the required salt, and then fixing the dye by adding alkali, with the aim of optimising the relation between physical adsorption and chemical reactivity. A method (M1) for dyeing cellulose fibres by the extraction process with reactive dyes of the vinylsulfone (VS) type, in which, to produce uniform and high dye adsorption, the dye bath is treated in presence of the textile material (before adding the fixer alkali) with the optionally required textile auxiliary substance, followed by the dyestuff and then (after its dispersion through all the liquid) a buffer for pH 7-10, and finally the required salt (in portions or continuously), after which the dye is fixed by adding alkali, in order to optimise the relationship between physical adsorption and chemical reactivity. An independent claim is included for a method (M2) for the boiling saponification of reactive dyes on cellulose fibres (further treatment to remove hydrolysed dye), in which the physical adsorption level is deliberately reduced by adding an adsorption-reducing auxiliary textile agent.

Description

For the dyeing of cellulose fibers after the exhaustion process can use a variety of reactive dye types with different Anchor groups are used, for. B. dyes of the VS (vinylsulfone) type (with Beta-sulfato-oxethyl-sulfone anchor or with vinyl sulfone anchor), of the DCT type (with di-chlorotriazine anchor), of the MCT type (with mono-chlorotriazine anchor), of the MFT type (with mono-fluoro-triazine anchor), of the MNT type (with monotinic acid triazine anchor), of the DFP type (with di-fluoro-pyrimidine anchor), of the DCC type (with di-chloro-quinoxaline anchor), of the TCP type (with trichloropyrimidine anchor) as well as dyes with multiple anchors such. B. VS / VS type dyes, VS / MCT type dyes, VS / MFT type, VS / DFP type, MCT / MCT type, VS / MCT / MCT type or the VS / VS / MCT type.

The Application of the reactive dyes by the exhaust process is done in aqueous dyeing liquor with the addition of salt (usually common salt or Glauber's salt) and of alkali depending on the anchor type at temperatures in the range of 40 to 90 ° C.

Becomes the dyeing is carried out at constant temperature (isothermal), the dyeing process is conducted in the current practice, that regardless of the dyeing unit (reel bucket, Jet, jigger, apparatus or tree) the textile goods in the required Amount of water is submitted at the appropriate temperature, whereupon in turn textile auxiliaries, salt, dye and finally Alkali be added. Exception: with large molecular weight Multi-anchor types will often only be part of the first Salt added, the addition of the remaining amount is then only after the addition of the dye. The addition of the alkali (indifferent whether it is di-Na-carbonate, Na-hydroxide, tri-Na-phosphate, Na-aluminate or mixtures of different compounds) takes place the isothermal dyeing proof linear-continuous or progressive-continuous over one Period of usually 15 to 45 minutes.

Becomes the dyeing is carried out according to the temperature step method, the addition of salt, dye and alkali takes place at room temperature, What to look for after a migration / equalization phase of 5 to 20 minutes from 20 to 60 minutes to the intended dyeing temperature is heated. Exception: for large-molecule multiple anchor types At first often only a part of the salt is added, the Addition of the remaining amount then takes place only after the achievement of the full Dyeing temperature.

This rough description of the dyeing process after the exhaustion process applies to all reactive dye types mentioned, it can be found in the sample cards and publications of the dye supplier (eg in the electronic sample card of DyStar Textile dyes GmbH & Co. KG Germany under www.DyStar.com ).

The Effect of the salt consists in principle in that first the physical adsorption of the reactive dye on the cellulose surface is brought about before the subsequent alkali then on the chemical fixation of the dye (at the point of adsorption) or as an unwanted side reaction to the hydrolysis of not adsorbed dye amount leads.

The mentioned colorings have a number of serious coloristic disadvantages:
It has been found that in many types of reactive dyes when the dye is added to the salt-containing liquor there is a great risk of an initial unegalality, since the salt concentration present leads to a rapid and intensive physical adsorption, especially of the first small amounts of dye. For the Ausegalisieren (migrate) of such a unegal adsorbed dye before the onset of alkali addition u. U. spent a lot of time or an excessive temperature.

Furthermore it turns out that the reactive dyes of the VS type as well as the VS multi-anchor types, which as a commodity in beta-sulfato-oxethyl-sulfone form, although have a comparatively low adsorption level that but this very much with the addition of the first (small) amounts of alkali quickly (within a few seconds or minutes) change to the vinyl form, resulting in a momentary sharp increase in the physical adsorption level leads. This always creates the great danger an initial unegalality. On top of that, the pH (before the beginning of the addition of the alkali) in practice usually neither controlled nor adjusted, so by the uncertain pH-ratios (influenced by the dyed material, through the available process water, through the dye, by the amount of dye) a limited Dyeing safety and poor reproducibility results especially in combination dyeings.

Furthermore, any experienced dyeing specialist knows that the percentage dye loss by Hy Drolyse at very high amounts of dye (over 3%, up to 10% based on the weight of the product) so much increases that after the usual Därbeweise no extremely high color depths (up to or over 2/1 standard depth) can be achieved. With such large quantities of dye used, very high dye losses result from hydrolysis, which leads to ecological problems in the form of strongly colored dyeing effluents and to economic disadvantages.

And It is an eternal practice problem that certain main dyes in a dyeing recipe certain nuancing components as well certain Nuanciernachsätze hardly or not at all come. In the case of such blocking phenomena, a colorimetric Recipe determination only to an unsatisfactory accuracy to lead.

It It is also known that reactive dyes with a very high water solubility (In particular, this applies under the conditions prior to the addition of the Alkalis also for VS types) only to a limited adsorption level and subsequently lead to an unsatisfactory fixation yield. An improvement can only be achieved by using increased Salt quantities, but not ecologically desirable is. In particular, the problem of unsatisfactory physical occurs Adsorption and a poor Fixierausbeute in the case of small molecular weight VS types, but also z. B. VS / VS double anchor types from the series the dioxazine dyes such. B. Color Index Reactive Blue 224 on.

Often have certain single dyes of a reactive dye trade range moreover, such untypical physical adsorption behavior, that these are not for combinations with other assortment products are fully suitable. There is then the desire to such individual dyes through targeted changes in the chemical constitution to give lower or higher adsorption level, d. H. in an optimal relation to the chemical reactivity without forfeiting other (good) product features. To the Example meets this problem in the assortment of VS types for Color Index Reactive Black 31 (very strong adsorption) and for Color Index Reactive Orange 107 and Color Index Reactive Red 23 (both very low adsorption) too.

It There was an urgent need for an overcoming the problems mentioned.

Surprisingly, it has now been found that in the dyeing of cellulose fibers by the exhaustion process with reactive dyes of the VS-type or VS multi-anchor / mixed anchor type, a high and very uniform physical dye adsorption and ultimately a very uniform and high chemical dye fixation is achieved Dyeing bath (before the addition / addition of the alkali) in the following order with the recipe-related additives, ie if one optimally controls the physical adsorption behavior in relation to the chemical reactivity:
According to the invention, in the presence of the textile product, the aqueous dyebath is first of all mixed with the optionally required textile auxiliaries (eg wetting agent or deaerating agent / running-fold inhibitor), then with the VS dye, after its distribution over the entire dyeing liquor with a buffer for pH values between 7 and 10, preferably between 7 and 9 and finally in a linear-continuous or progressive-continuous manner (within a time period of 10 to 45 minutes, preferably 15 to 30 minutes) with the salt. According to the invention, the pH buffer can also be added after the salt addition. Following this, in a known manner by the method of the temperature stage dyeing process or the isothermal dyeing process by means of alkali at the required temperature, the dye fixation brought about.

to pH buffering according to the invention are organic and / or inorganic systems such. Sodium acetate, sodium hydrogen phosphate / dihydrogen phosphate, Sodium carbonate / bicarbonate, sodium borate / tetraborate / boric acid or other means, in an amount which until the beginning of the addition of the fixing alkali the desired maintains pH or pH range according to the invention. A pH buffer substance according to the invention can also already mixed by the manufacturer with the reactive commercial dye become.

Surprisingly was found that by the inventive Procedure especially for reactive dyes of the VS type and a VS multiple anchor / mixer anchor type in the beta-sulfato-oxethyl-sulfone form a uniform and even construction of a high physical adsorption levels is achieved, what then (after the addition of the fixing alkali) to a very good result the Egal color, the color structure and the Fixierausbeute leads. In other words: through this targeted control of the physical adsorption behavior in relation to the chemical Responsiveness of the dyes can be urgent practice requests in the reactive dyeing of cellulose fibers.

Also if the VS dyes or VS multi-anchor / mixed anchor dyes wholly or partially in the vinyl-sulfone form is by the procedure according to the invention a clear Improvement of equal color achieved.

According to the invention the addition / addition of the salt with the addition / addition of the fixing alkali in such a way that the Addition / addition of the fixing alkali already after the addition / addition a portion of the salt begins.

When advantageous for deep colorations proves the Use of a mixture or common solution of salt and fixing alkali for the dye fixing, wherein the Salt content can vary within a wide range. Advantageous is also the supplement of further salt after the addition / addition of the fixing alkali. In both cases one achieves increased maximum color depths (with increased fixation yield and lower hydrolysis loss).

When very valuable, the inventive proves Procedure when mixing mixtures of two colors or the same color similar reactive dyes used, the first component a reactive dye of the VS type or a VS multi-anchor / mixing anchor type represents and the second component is a reactive dye of a Non-VS type represents what a physical adsorption level which is between the vinyl sulfone form of the first Reactive dye and that of its hydrolyzate. As special valuable turns out when the physical adsorption level the second reactive dye in the middle between said Limits. Such non-VS type dyes include z. B. reactive dyes of the MFT (mono-fluoro-triazine) type and the DCC (di-chloro-quinoxaline) type. Even more valuable regarding the uniform construction of a high physical Adsorption levels and ultimately in terms of maximum Fixierausbeute are corresponding mixtures of two Farbtongleichen or -like reactive dyes whose second component is a reactive dye of a non-VS type, which is a lower chemical reactivity (fixation / hydrolysis rate) has as the first component. To such dyes of the non-VS type belong z. B. reactive dyes of the MCT (mono-chloro-triazine) type or the DCC (di-chloro-quinoxaline) type.

According to the invention also corresponding mixtures of reactive dyes of the VS type and / or a VS mixing anchor / multi-anchor type are used in which the VS mixing anchor / multiple anchor component in beta-sulfato-oxethyl-sulfone form and the pure VS component is present in vinyl sulfone form. In such Cases will be a strong approximation of both components concerning uniform attainment achieved a high physical Adsorptionsniveaus.

When very advantageous in terms of achieving a high physical Adsorption levels turn out to be mixtures of two or more two identical or similar reactive dyes of the VS type or of a VS mixing anchor / multiple anchor type in quantity ratios of at least 25, not more than 75% per individual dye individual Water solubility as a result of a reduced by one number of sulfo groups is not fully sufficient for practical use. In particular, this applies if the dyes mentioned in the beta-sulfato-oxethyl-sulfone form available. Voraussetzuing here is still that the individual dyes (in the beta-sulfato-oxethyl-sulfone form) in the neutral pH range a water solubility at 50 ° C in the range of 10 to 30 g / l.

The inventive method of optimized Control of physical adsorption in relation to chemical Responsiveness is especially valuable when in the case of combination dyeings small amounts of one or more Shading component (s), provided that the nuancing component (s) an equal or slightly higher physical Adsorption level as / as the major component (s). Just In this way, in addition to a good Egalfärbung one high accuracy achieved in the colorimetric recipe calculation because of the dreaded blocking of nuancing components is avoided.

For Shading etchants are said (for the same reason) to be dyes with a slightly higher physical adsorption level than that of the main component.

Surprisingly, it has also been found that one achieves a uniform and level structure of a high physical adsorption levels, when using the salt or Glauber's salt usually used as salt by a stoichiometric amount of a potassium salt such. As potassium chloride or potassium sulfate replaced. Even a partial replacement of sodium salts with potassium salts leads to an increase in the physical adsorption level. The same result is also obtained when sodium verbin In the case of the pH buffer system or the fixing alkali, it can be replaced completely or partially by the corresponding potassium compounds.

Surprisingly For example, the enhancement effect by the potassium compounds is dye-specific. A particularly high effect is achieved with reactive dyes of the VS or VS / VS dioxazine type, e.g. Eg at Color Index Reactive Blue 224, whether in beta-sulfato-oxethyl-sulfone form or in vinyl sulfone form. About this invention The findings are reactive dyes of the VS or the VS / VS dioxazine type such as B. Color Index Reactive Blue 224 well combinable with reactive dyes of VS / VS type such as B. Color Index Reactive Black 5 or Color Index Reactive Blue 203, giving the even and level As far as high physical adsorption levels are concerned, and resulting in high Fixierausbeute to valuable dark blue shades leads.

For Achieving a particularly high overall physical adsorption level can according to the invention described Operation even after an already partially completed addition / addition be added by fixing alkali further reactive dye, possibly together with (or followed by) additional salt and / or Alkaline gifts. This reactive dye to be replenished may be of the VS type, VS anchor / multiple anchor type or non-VS type. Particularly advantageous is the Nachsatz of dyes, which a have higher physical adsorption level than the hydrolyzate of the initially used reactive dye. This procedure leads to a color build up to highest color depths and a high overall fixation yield.

Especially valuable is the procedure according to the invention in their full width in the case of combination dyeings, when the physical adsorption level and the chemical reactivity (Fixation or hydrolysis) in a perfect relation to each other stand. If you perform a chromatographic experiment simultaneous determination of the physical adsorption level and the chemical fixation speed through, should be the same or similar "fixing profile" for all combination partners result, especially if conditioned by the dye or the dyeing machine with egalitarian problems is to be expected.

The Cellulose fibers to be dyed according to the invention include cotton, launded or mercerized cotton, regenerated cellulose and linen, whether or not in the form of mixtures with one another and with other fibers, as other fibers, especially polyester and polyacrylonitrile fibers be considered. The textile can in all packaging forms present, in particular in the form of fabrics, knitted fabrics, yarns, Kammzug and loose material.

The Reactive dyes to be used according to the invention can be in the form of powders, granules or liquid preparations available.

The Post-treatment of the dyeings produced according to the invention (after the chemical fixation of the dye by means of alkali) in the usual way by rinsing with cold and warm water, boiling soaps and rinsing again with warm and cold water, with the last rinse a Addition of acetic acid may contain. The boiling soaps can also by using the inventive concept (in particular in Dyeings in high color depth) so happened that the physical Adsorption level of the dye hydrolyzate is deliberately lowered. For this purpose, the boiling soap bath according to the invention a adsorption-reducing textile auxiliaries z. B. based on polyvinyl pyrrolidone in quantities (depending on dyed color depth and depending on the liquor ratio) from 0.2 to 5 g / l, preferably from 0.5 to 2 g / l, wherein the pH is between 5 and 9, preferably between 7 and 8 should. This aftertreatment leads to a faster and more complete washing out of the dye hydrolyzate and thus to save time and water as well as to improve the washing, Water and perspiration fastness.

The The following examples serve to illustrate the concept of the invention:

Example 1:

A bleached cotton fabric is preceded on a winch bucket at a FV (liquor ratio) of 1:35 and at a temperature of 45 to 50 ° C for uniform meshing for 10 minutes. There are 2% (based on the weight of the product) of a commercially available reactive dye CI type (Color Index) Reactive Orange 107 in dissolved form and then within 10 minutes 2 g / l Na acetate add, with a pH of 7.5 to 8 sets. Then 50 g / l Na chloride are added over a period of 15 minutes in 5 equal portions, resulting in a high and uniform physical dyestuff sorption leads. Now, within 45 minutes, progressive-progressive (with 50% progression) 5 g / l Na-carbonate calc. (Soda) and 1.5 ml / l Na hydroxide 50% in the form of a common solution added. After another 30 minutes, the dye fixation is complete. The coloring is completed as usual by cold and warm rinsing, boiling soaps with 0.5 ml / l acetic acid 60%, repeated warm and cold soaps. It results in high Fixierausbeute a golden yellow coloration of very good levelness.

Example 2:

One Yarn made from mercerised cotton in the form of X-coils is included Room temperature in a FV 1: 8 in a yarn dyeing machine submitted. It will be 0.5% of a commercially available reactive dye C.I. Reactive Red 23 (in dissolved form) and subsequently 1 g / l of a 3: 1 mixture of di-Na hydrogen phosphate and Na dihydrogen phosphate added, with a pH between 8.5 and 9.5 sets. Then within 15 minutes 50 g / l Glauber's salt in the form an aqueous solution added linear-continuous and after a further 15 minutes 5 g / l Na carbonate calc. and 0.5 ml / l Na hydroxide 50%. It is heated to 40 ° C in 40 minutes and colored within another 30 minutes. In a good fixation yield, a pink color is obtained with perfect levelness.

Example 3:

One dyed fabric consisting of 65% cotton and 35% Polyester fibers will be on the jet at FV 1: 5 and at 60 ° C submitted and initially with 8% (by weight the cotton) of a commercially available reactive dye C.I. Reactive Blue 220 added. The pH is 2 g / l of a 2: 1 mixture of borax and boric acid adjusted to 8 to 8.5. about a period of 20 minutes become 80 g / l Na-chloride linear-continuous interspersed. Then progressively-continuously (with 50% progression) 10 g / l of tri-Na-phosphate in the form of an aqueous solution in 30 minutes Added solution. After dyeing out the dye within 45 minutes at 60 ° C, the staining becomes finished as usual. You get on the Cotton content a deep blue color in very good Fixierausbeute.

Example 4:

One Viscose fiber is knitted on the jet at a FV of 1: 6 submitted at 50 ° C. It will successively 6% (relative on the weight of the product) of a reactive dye C.I. Reactive Red 180 and after its uniform distribution over the entire dye liquor 1 g / l of a 5: 1 mixture of sodium bicarbonate and Na carbonate calc. added. After 15 minutes falls The pH of about 9 to about 8, and you dosed within 20 minutes progressive-continuous (70% progression) 50 g / l Na-chloride in the form of a 35% aqueous solution. To 15 minutes will be progressive within 45 minutes (30% progression) 10 g / l Na carbonate calc. added. After another 30 minutes the dye fixation is complete. You get after usual completion a deep red color, which is characterized by a very good Fixierausbeute and by a very good levelness distinguishes.

Example 5:

One Yarn of mercerized cotton in strand form is used in a yarn dyeing machine submitted at FV 1:15 at 50 ° C. After addition of 1% (based on the weight of the product) of a commercially available reactive dye C.I. Reactive Yellow 15 becomes 20 g / l within 15 minutes Glauber's salt was added, whereupon the pH by means of 1 g / l Na bicarbonate is set to 7.5. After another 15 minutes, the pH is about 7 dropped off, and it is a tall and even physical dye adsorption came about. As with the isothermal coloring proofs are common now within of 30 minutes 10 g / l Na carbonate calc. in the form of an aqueous Solution by progressive dosage (70% progression) added. After dyeing out the dye and completion one obtains in very good Fixierausbeute a completely level yellow color.

Example 6:

A cotton fabric is dyed at FV 1:30 at 40 ° C on a winch blade in the following manner: First, add 4% (by weight) of commercially available reactive dye CI Reactive Black 5 and Reactive Blue 203, adjust and maintain a pH from 8 to 8.5 by means of borax, finally continuous addition of 80 g / l Na chloride. Approximately 10 minutes after these additions, the usual progressive-continuous addition (50% progression) of 5 g / l Na carbonate calc. Begins. and 2 g / l Na hydroxide in the form of a common aqueous solution. After another 30 minutes, rinsing, Soaps, rinsing finished again. With very good fixation yield and levelness, a deep navy blue color is obtained.

Example 7:

used one according to the data in example 6 5% (related to the weight of the goods) of a commercially available reactive dye C.I. Reactive Red 198, so also obtained with very good Fixierausbeute and very good levelness a deep red color.

Example 8:

you sets 0.8% (based on the weight of goods) of a commercial one Reactive Dye C.I. Reactive Violet 5 (albeit in vinyl form instead of the commercial Betasulfatooxethylsulfon form) within 15 minutes at FV 1:12, 60 ° C, pH 7 one submitted to cotton fabric. Then be within 20 minutes 10 g / l Glauber's salt in 5 equal portions added, taking one a uniform physical adsorption, d. H. achieves a high (physical) initiality. To the usual fixation using Na carbonate / Na hydroxide and the completion of the dyeing is obtained a completely level violet coloration.

Example 9:

One Linen fabric is added after the isothermal dyeing test 70 ° C in a dyeing tree at FV 1: 6 submitted. After the addition of 3% (by weight of the product) of a commercial Reactive Dye C.I. Reactive Yellow 176 and after a circulation time of 15 minutes, 0.5 g / l Na-acetate and borax are added. After a further 15 minutes, 40 g / l Na chloride are obtained within 15 minutes added. Then within 15 minutes 15 g / l Na carbonate calc. in the form of an aqueous solution linear-continuous metered in and after another 30 minutes again 20 g / l Na chloride and 5 g / l Na carbonate calc. Obtained in high Fixierausbeute and with good levelness a deep golden yellow color.

Example 10:

causticized Cotton is in FV 1:10 at 50 ° C along with 2% of a Commercially available reactive dye C.I. Reactive Yellow 37 submitted. One makes with Na-bicarbonate / -Na-carbonate one pH of 8.5 and dosed within 20 minutes in progressive Form (70% progression) 30 g / l Na-chloride too. After another 10 minutes you start with a progressive addition (50% progression) an aqueous solution of tri-Na-phosphate and Na chloride (in the ratio 1: 1) in an amount which total to 10 g / l tri-Na-phosphate and 40 g / l Na-chloride leads. This gives a completely level yellow color.

Example 11:

you created at FV 1:30, 50 ° C a stain of bleached Cotton with 6% of a commercially available reactive dye C.I. Reactive Orange 82, with the pH at 8.5 in turn placed, then 60 g / l Glauber's salt was added, the fixing alkali added and finally 20 g / l Glauber's salt are added. This gives a deep, level rotorange staining.

Example 12:

A dyebath is used at FV 1:20, 50 ° C., containing bleached cotton fabric, 0.5 g / l of a commercial wetting agent and 2% (based on the weight of goods) of 3 reactive dyes of the following constitution:

To the uniform distribution of the dyes over the entire dye liquor is mixed with 1 g / l Na-acetate on a pH of about 7.5 to 8 provided. After 20 minutes you enter inside for a further 20 minutes 50 g / l Na chloride to, with a high and uniform physical dye adsorption results. Now be within 30 minutes on linear-continuous 5 g / l Na carbonate calc. and 2 g / l Na hydroxide 50% added, and the fixation will be completed after another 30 minutes. you gets a deep orange color with very good fixation yield.

Example 13:

versetzt. Der pH-Wert wird mittels Na-Hydrogencarbonat/Na-Carbonat auf 8 bis 9 eingestellt. Nach 15 Minuten werden 80 g/l Glaubersalz portionsweise zugegeben. Nach weiteren 15 Minuten werden innerhalb von 30 Minuten (mit 50% Progression) 10 g/l Tri-Na-Phosphat als wässrige Lösung zudosiert. Nach der Beendigung der Farbstofffixierung erhält man mit sehr hoher Fixierausbeute eine tiefe, egale Goldgelb-Färbung. Anmerkung zu den relativen Adsorptionswerten 100 (1-RF), chromatographisch auf Zellstoff mit 5 g/l Na-Chlorid bei 50°C: Farbstoff I in Ester-Form 55 in Vinyl-Form 85 als Hydrolysat 65 Farbstoff II 75 A jet dye on bleached cotton fabric becomes FV 1: 8 at 70 ° C with 3% (based on the fabric weight) of 2 reactive dyes of the constitutions

added. The pH is adjusted to 8 to 9 using Na bicarbonate / Na carbonate. After 15 minutes, 80 g / l Glauber's salt are added in portions. After another 15 minutes 10 g / l Tri-Na-phosphate are added as an aqueous solution within 30 minutes (with 50% progression). After completion of the dye fixation, a deep, level gold yellow color is obtained with very high fixation yield. Remarks on the relative adsorption values 100 (1-RF), chromatographically on pulp with 5 g / l Na-chloride at 50 ° C: Dye I in ester form 55 in vinyl form 85 as a hydrolyzate 65 Dye II 75

Example 14:

zugesetzt, und nach kurzer Zeit wird der pH-Wert mittels Borax/Borsäure auf 8.5 gestellt. Nach 15 Minuten werden 25 g/l Na-Chlorid zugegeben, nach weiteren 15 Minuten innerhalb von 30 Minuten 10 g/l Na-Carbonat calc. und innerhalb von weiteren 30 Minuten als gemeinsame Lösung 10 g/l Na-Carbonat calc. und 25 g/l Na-Chlorid linear zudosiert. Nach abgeschlossener Farbstofffixierung und nach Fertigstellung wie üblich erhält man eine tiefe Rot-Färbung bei einer sehr hohen Fixierausbeute und einer sehr guten Egalität. Anmerkung zu den relativen Adsorptionswerten 100 (1-RF), chromatographisch auf Zellstoff mit 2 g/l Na-Chlorid bei 60°C: Farbstoff in Ester-Form 60 in Vinyl-Form 80 als VS-Hydrolysat 70 als VS-Hydrolysat 80 (mit doppelter Salzkonzentration) Bleached cotton is submitted at FV 1:25, 70 ° C. There are 6% (by weight of the product) of a reactive dye of the constitution

is added, and after a short time the pH is adjusted to 8.5 by means of borax / boric acid. After 15 minutes, 25 g / l Na-chloride are added, after a further 15 minutes within 30 minutes 10 g / l Na carbonate calc. and within a further 30 minutes as a common solution 10 g / l Na carbonate calc. and 25 g / l Na chloride added linearly. After completion of dye fixation and after completion as usual, a deep red color is obtained with a very high fixation yield and a very good levelness. Remarks on the relative adsorption values 100 (1-RF), chromatographically on pulp with 2 g / l Na-chloride at 60 ° C: dye in ester form 60 in vinyl form 80 as VS-hydrolyzate 70 as VS-hydrolyzate 80 (with double Salt concentration)

Example 15:

The procedure is as described in Example 13, but with reactive dyes of the Constitutions

It results in a deep red color, characterized by a very high fixation yield and a very good levelness.

Example 16:

• a) 4% C. I. Reactive Blue 220 + 0.5% C. I. Reactive Blue 203 (als Nuancierkomponente)
• b) 4% C. I. Reactive Black 5 mit 0.5% C. I. Reactive Blue 203 (als Nuanciernachsatz)

Colored bleached cotton is dyed after isothermal dyeing (50 ° C., initial pH 8.5, 80 g / l Na chloride, Na carbonate / Na hydroxide as fixing alkali)

• a) 4% CI Reactive Blue 220 + 0.5% CI Reactive Blue 203 (as shading component)
• b) 4% CI Reactive Black 5 with 0.5% CI Reactive Blue 203 (as Nuanciernachsatz)

• c) 4% C. I. Reactive Black 31 + 0.5% C. I. Reactive Violet 5 (als Nuancierkomponente)
• d) 4% C. I. Reactive Black 31 mit 0.5% C. I. Reactive Violet 5 (als Nuanciernachsatz)

There are no blocking phenomena in both cases a) and b).

• c) 4% CI Reactive Black 31 + 0.5% CI Reactive Violet 5 (as shading component)
• d) 4% CI Reactive Black 31 with 0.5% CI Reactive Violet 5 (as Nuanciernachsatz)

In Cases c) and d) is the fixation of Reactive Violet 5 almost completely blocked.

Note on the adsorption values 100 (1-RF), chromatographed on pulp with 2 g / l Na-chloride at 50 ° C, respectively given for the vinyl form, ie at pH 8 to 8.5: CI Reactive Black 5 80 CI Reactive Blue 220 75 CI Reactive Blue 203 85 CI Reactive Black 31 98 CI Reactive Violet 5 60

Example 17:

• a) Konventionelle Färbeweise: Zuerst Zugabe 50 g/l Na-Chlorid, dann Zugabe Farbstoff, nach 10 Minuten progressive Dosierung (50% Progression) innerhalb von 30 Minuten von 8 g/l Na-Carbonat calc., Ausfixierung, Fertigstellung.
• b) Erfindungsgemäße Färbeweise: Zuerst Zugabe Farbstoff, dann Zugabe 1 g/l Na-Hydrogencarbonat/Na-Carbonat calc. im Verhältnis 1:1 (für pH 8 bis 9), nach 10 Minuten Zugabe von 50 g/l Na-Chlorid, nach weiteren 10 Minuten progressive Dosierung (50% Progression) innerhalb von 30 Minuten von 8 g/l Na-Carbonat calc., Ausfixierung, Fertigstellung.
• c) Verbesserte erfindungsgemäße Färbeweise: Durchführung wie unter b) angegeben, aber unter Ersatz der 50 g/l Na-Chlorid durch 35 g/l Na-Chlorid plus 20 g/l K-Chlorid.
• d) Optimale erfindungsgemäße Färbeweise: Durchführung wie unter b) angegeben, aber unter Ersatz von 50 g/l Na-Chlorid durch 60 g/l K-Chlorid.

Dyeing on bleached cotton after isothermal dyeing proof at FV 1:12, 50 ° C. with 4% (based on the product weight) of a commercially available reactive dye CI Reactive Blue 224 according to the following variants:

• a) Conventional staining procedure: first add 50 g / l Na chloride, then add dye, after 10 minutes progressive dosing (50% progression) within 30 minutes of 8 g / l Na carbonate calc., Ausfixie tion, completion.
• b) dyeing method according to the invention: first adding dye, then adding 1 g / l Na bicarbonate / Na carbonate calc. in the ratio 1: 1 (for pH 8 to 9), after 10 minutes addition of 50 g / l Na chloride, after another 10 minutes progressive dosage (50% progression) within 30 minutes of 8 g / l Na carbonate calc ., Fixation, completion.
• c) Improved dyeing method according to the invention: Carrying out as indicated under b), but replacing the 50 g / l Na-chloride with 35 g / l Na-chloride plus 20 g / l K-chloride.
• d) Optimal dyeing method according to the invention: carrying out as indicated under b), but substituting 50 g / l Na chloride with 60 g / l K chloride.

To the modes b) and in particular c) and d) receives one substantially deeper blue colorations than after the conventional one Procedure a), with simultaneous reduction of staining waste water and at the same time improving the dyeing

Example 18:

bleached Cotton is submitted at room temperature in a 1:25 FV and with 2% (based on the weight of the goods) of a commercial one Reactive dye C.I. Reactive Blue 224 and 2% (based on the Weight of the product) of a commercially available reactive dye C. I. Reactive Blue 220 added. The pH is adjusted by means of 1 g / l Na bicarbonate set to 8 to 8.5. There are added 40 g / l K-sulfate, and It is heated to 60 ° C in 30 minutes. Well be linear-continuous 12 g / l tri-K-phosphate within 30 minutes Form added to an aqueous solution. After 45 Minutes at 60 ° C, the dye fixation is completed. After usual Completion gives you a particularly deep blue color in very good levelness.

Example 19 to 32:

modified commercially available reactive dyes (standard) with the Aim of an optimized physical adsorption value, so receives with virtually unchanged basic properties (such as color, Light fastness, chemical resistance) by an improved Relation of physical adsorption behavior and chemical Responsiveness a significant improvement in the dyeing properties.

Example 19: Standard C.I. Reactive Yellow 15

Increased physical adsorption level in conjunction with increased chemical reactivity leads, with subsequent modification, to improving the fixation yield and the hydrolyzate leachability:

Example 20: Standard C.I. Reactive Yellow 37

Increased physical adsorption level by subsequent modification leads to significant improvement in fixation yield:

Example 21: Standard C.I. Reactive Orange 82

Increased physical adsorption level by subsequent modification leads to significant improvement in fixation yield:

Example 22: Standard C.I. Reactive Violet 5

Increased physical adsorption level by subsequent modification leads to a marked improvement in fixation yield and color build-up, but with a bluer hue:

Example 23: Standard C.I. Reactive Orange 107

Moderately increased physical adsorption level through subsequent modification leads to moderate improvement in fixation yield, but with a redder hue:

Example 24: Standard C.I. Reactive Red 174

Increased physical adsorption level by subsequent modification leads to an improvement in the fixing yield and the color composition, but with a blue shade:

Example 25: Standard C.I. Reactive Red 194

Moderately increased physical adsorption level through subsequent modification leads to moderate improvement in fixation yield and color build-up:

Example 26: Standard C.I. Reactive Red 198

Increased physical adsorption level by subsequent modification leads to improvement of fixation yield and color build-up:

Example 27: Standard C.I. Reactive Blue 49

Increased physical adsorption level and increased chemical reactivity lead to substantial improvement of fixation yield and color build-up by subsequent modification:

Example 28: Standard C.I. Reactive Blue 194

Increased physical adsorption level by subsequent modification leads to the improvement of fixation yield and equal coloration:

Example 29: Standard C.I. Reactive Blue 221

Moderately increased physical adsorption level by subsequent modification leads to a moderate improvement in the fixation yield:

Example 30: Standard C.I. Reactive Blue 224

Increased physical adsorption level by subsequent modification leads to a marked improvement in fixation yield and color build-up:

Example 31: Standard C.I. Reactive Blue 225

Moderately increased physical adsorption level by subsequent modification leads to moderate improvement of fixation yield and color build-up with simultaneous improvement of the level dyeing:

Example 32: Standard C.I. Reactive Black 31

Moderately reduced physical adsorption level by subsequent modification leads to the improvement of the Egalfärbeverhaltens:

More reduced physical adsorption level by subsequent modification leads to substantial improvement of the equal dyeing behavior:

Example 33:

• a) 0.5 g/l Essigsäure 60%ig
• b) 1 g/l eines handelsüblichen Entsubstantivierungsmittels des Typs Polyvinylpyrrolidon und 0.5 g/l Essigsäure 60%ig
• c) 1 g/l eines handelsüblichen Entsubstantivierungsmittels des Typs Polyvinylpyrrolidon und 0.5 g/l Ammoniak 30%ig

Is carried out in the usual manner by the isothermal exhaust method at FV 1:10, 60 ° C a dyeing of bleached cotton with 8% (based on the weight of goods) of a commercially available reactive dye CI Reactive Red 180 by. Completion of staining after fixation is complete by rinsing with cold and warm water followed by a boiling soapy for 15 minutes

• a) 0.5 g / l acetic acid 60%
• b) 1 g / l of a commercial Entsubstantivierungsmittels type polyvinylpyrrolidone and 0.5 g / l acetic acid 60%
• c) 1 g / l of a commercial Entsubstantivierungsmittels type polyvinylpyrrolidone and 0.5 g / l ammonia 30%

Subsequently is rinsed warm and cold, with the last rinse an addition of 0.25 g / l acetic acid 60%. One obtains to b) and especially to c) a much better Washability of the dye hydrolyzate as conventional Method a).

Example 34:

Is working as described in Example 33, but with a commercial one Reactive dye C.I. Reactive Blue 160, so you get a corresponding Result.

Example 35:

A chromatogram is generated in duplicate using the following parameters: Stationary phase commercially available chromatography paper (pulp) Test substance (starting point) aqueous solution of 0.5 g / l CI Reactive Blue 224 (Vinylsulfone form) and 0.5 g / l CI Reactive Black 31 Mobile phase aqueous solution of 5 g / l Na chloride, 5 g / l Na carbonate calc., 1 ml / l Na hydroxide 50% temperature 60 ° C

One The two chromatograms are tel quel after drying with respect to the color intensity from the starting point to the solvent front scanned. The other one is (careful) several times with boiling hot water treated, with unfixed dye moieties and the dye hydrolysates are washed out, then also scanned after drying. It is found that both dyes used homogeneously in a RF values have been fixed in the range between 0.05 to 0.15, where In this area a nearly uniform dark blue emerged is. By comparison of the soaped and the soaped chromatogram results a fixation yield of 94%. The combinability under consideration the relation of physical adsorption level and chemical Responsiveness is so near perfect, you will too achieve a good equality in practice.

Example 36:

*

Die Ermittlung eines erfindungsgemäß geforderten bestimmten physikalischen Adsorptionsniveaus/-verhaltens kann auf die unter (a) oder (b) beschriebene Weise geschehen:

a

Man chromatographiert den/die zu bestimmenden Reaktivfarbstoff(e) unter Verwendung von Zellulose in Form von Zellstoff, von Baumwolle oder von Baumwoll-Linters nach der Methode der paper chromatography (PC), der thin layer chromatography (TLC) oder der high performance liquid chromatography (HPLC) als stationäre Phase und einer 0.1 bis 5%igen wässrigen Kochsalz-Lösung (für schwach adsorbierende Farbstoffe) bzw. einer 0.01 bis 0.5%igen wässrigen Kochsalz-Lösung (für stärker adsorbierende Farbstoffe) als mobile Phase bei Temperaturen zwischen 20 und 80°C.

b

Alternativ chromatographiert man den/die zu bestimmenden Reaktivfarbstoff(e) unter Verwendung von Zellulose in Form von Zellstoff, von Baumwolle oder von Baumwoll-Linters nach der PC- oder der TLC-Methode als stationäre Phase und einer wässrigen Lösung, enthaltend 1 bis 50 g/l Kochsalz und 0.01 bis 10 g/l Reaktivfarbstoff (für schwach bzw. stärker adsorbierende Farbstoffe) als mobile Phase bei Temperaturen zwischen 20 und 80°C.

If, according to the information in Example 35, but using a test substance (order to the starting point) from an aqueous solution of 1.5 g / l CI Reactive Red 180 and 0.5 g / l CI Reactive Violet 5, it is finally found that the Red dye has been fixed at an RF value in the range of 0.08 to 0.18 and the violet dye at an RF value in the range of 0.10 to 0.70. The combinability is due to this bad relation of physical adsorption and chemical reactivity too It is so bad that under unfavorable equipment or material-related conditions of practice great equivalency problems can be expected.

*

The determination of a particular physical adsorption level / behavior required according to the invention can be carried out in the manner described under (a) or (b):

a

The reactive dye (s) to be determined are chromatographed using cellulose in the form of pulp, cotton or cotton linters by the method of paper chromatography (PC), thin layer chromatography (TLC) or high performance liquid chromatography (HPLC) as a stationary phase and a 0.1 to 5% aqueous sodium chloride solution (for weak adsorbing dyes) or a 0.01 to 0.5% aqueous sodium chloride solution (for more strongly adsorbed dyes) as a mobile phase at temperatures between 20 and 80 ° C.

b

Alternatively, the reactive dye (s) to be determined are chromatographed using cellulosic pulp, cotton or cotton linters by the PC or TLC method as a stationary phase and an aqueous solution containing 1 to 50 g / l common salt and 0.01 to 10 g / l reactive dye (for weakly or more strongly adsorbing dyes) as mobile phase at temperatures between 20 and 80 ° C.

in the Case (a) is formed from the RF value of the obtained color spot the Adsorption value 100 (1-RF), which numbers between 0 and 100 can assume, with a low value for a weak one and a high value for strong adsorption.

**

Die Ermittlung des erfindungsgemäßen „Fixier-Profils” kann auf die unter c) beschriebene Weise geschehen:

c

Man verfährt nach der PC- oder der TLC-Methode unter Verwendung von Zellulose in Form von Zellstoff Baumwolle oder von Baumwoll-Linters als stationäre Phase und unter Verwendung einer frisch hergestellten wässrigen Lösung, enthaltend 1 bis 50 g/l Kochsalz, 0.01 bis 10 g/l Reaktivfarbstoff und ein adäquates (praxisgemäßes) Alkali als mobile Phase bei Temperaturen zwischen 40 und 80°C.

In the case (b), from the RF value of the color front, the adsorption value 100 (1-RF) is formed, which can also assume values between 0 and 100, and which, in addition to the case (a), takes into account the effect of the dye concentration ,

**

The determination of the "fixing profile" according to the invention can be carried out in the manner described under c):

c

The process is carried out by the PC or TLC method using cellulose pulp cotton or cotton linters as stationary phase and using a freshly prepared aqueous solution containing 1 to 50 g / l of common salt, 0.01 to 10 g / l Reactive dye and an adequate (practical) alkali as a mobile phase at temperatures between 40 and 80 ° C.

The in case c) obtained fixation chromatogram shows chemically fixed Dye, dye hydrolyzate and optionally residual amounts intact reactive dye. The fixation chromatogram is compared to the Color intensities and RF values scanned. Subsequently dye hydrolyzate and intact reactive dye are carefully Washed out with boiling hot water. The washed Fixing chromatogram contains only chemically fixed dye will be scanned again.

Of the scanned course of the washed chromatogram compared to Scanned the course of the unwashed represents the "fixing profile" or the "hydrolysis profile" of a reactive dye (or a reactive dye combination). The Fixierausbeute can be calculated by comparing the scanned values of both chromatograms calculate mathematically.

Annotation:

The Methods for determining a required according to the invention specific (physical) adsorption behavior / levels * and for determining an inventively required Fixing profiles ** are part of the present patent application.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited non-patent literature

• - www.DyStar.com [0005]

Claims (35)

A process for dyeing cellulose fibers by the exhaust process with reactive dyes of the VS (vinylsulfone) type, characterized in that to achieve a uniform and high physical Farbstoffadsorption * the dyebath before the addition / addition of the fixing alkali in the presence of the textile in turn with the optionally required textile auxiliaries, then with the dye, then after its distribution over the entire dyeing liquor with a buffer for a pH between 7 and 10 and finally added portionwise or continuously with the required salt, whereupon as usual by means of alkali addition the Dye fixation initiated / carried out with the aim of an optimally controlled relation of physical adsorption and chemical reactivity. Process according to claim 1, characterized characterized in that by the isothermal staining method (at constant temperature) with a buffer for one pH is worked between 7 and 9. Process according to claim 1, characterized characterized in that after the temperature step method (under warm up the dye liquor) is worked, the dyebath before the addition of the fixing alkali at room temperature in order with the optionally required textile auxiliaries, then with the dye its distribution over the entire dyeing liquor with a buffer for a pH between 8 and 10 and finally in portions or continuously with the required Salt is added, as usual, the dye fixation by means of alkali addition and heating to dyeing temperature initiated / carried out. Process according to claims 1 to 3, characterized in that the salt is progressively-continuous as Solid or is added as an aqueous solution. Process according to claims 1 and 4, characterized in that the pH buffer after the Addition of the salt is added. Process according to claims 1 to 5, characterized in that reactive dyes of a VS (vinylsulfone) Mehrfachanker type be used. Process according to claim 6, characterized in that reactive dyes of the VS / VS (vinylsulfone) double anchor type be used. Process according to claim 6, characterized characterized in that reactive dyes of VS (vinylsulfone) / MCT (monochlorotriazine) - or the VS / MFT (monofluorotriazine) double anchor type Process according to claims 1 to 8, characterized in that the VS (vinylsulfone) anchor in beta-sulfato-oxethyl-sulfone form is present. Process according to claims 1 to 8, characterized in that mixtures of dyes with the VS (vinylsulfone) anchor in beta-sulfato-oxethyl-sulfone form and in vinyl sulfone form. Process according to claims 1 to 3, characterized in that organic and / or as a pH buffer inorganic systems such. B. Na acetate, Na hydrogen phosphate / dihydrogen phosphate, Na carbonate / bicarbonate, Na borate / tetraborate / boric acid used in an amount that until the onset of addition of the fixing alkalis of the set pH / range maintained becomes. Process according to claim 2, characterized characterized in that the addition / addition of the salt and the addition / addition Alkalis overlap in such a way that the dosing of the alkali already after the addition of 50 to 90% of the salt starts. Process according to claim 2, characterized characterized in that the chemical dye fixing a mixture / solution of salt and alkali is used. Process according to claim 2, characterized characterized in that after the addition of the alkali another Amount of salt is added. Process according to Claims 1 to 14, characterized in that mixtures of two inks of the same color or the same color are used, the first component of which represents a reactive dye of the VS (vinylsulfone) type, the VS / VS type or a VS / mixed anchor type, and their second component te represents a reactive dye of the non-VS type, which has a physical adsorption *, which lies between the level of the vinyl sulfone form of the first dye and that of its hydrolyzate. A method according to claim 15, characterized characterized in that the reactive dye of the non-VS type is a physical Adsorption level *, which is in the middle (+/- 10%) between the level of the vinyl sulfone form of the first dye and that of its hydrolyzate. Process according to claims 15 and 16, characterized in that the second component is a reactive dye of the non-VS type, which has a lower chemical reactivity (Fixing / hydrolysis rate) than the first component. A method according to claim 17, characterized characterized in that the second component is a reactive dye of the MCT (monochlorotriazine) type or MCT / MCT double anchor type represents. Process according to claims 1 to 14, characterized in that mixtures of farbtongleichen or similar reactive dyes of the VS (vinylsulfone) type used, the second component of which has a lower chemical reactivity has as the first component. A method according to claim 17, characterized characterized in that the second component is a reactive dye of the DCC (dichloroquinoxaline) type. A method according to claim 17, characterized characterized in that the second component is a reactive dye of the MNT (mononicotinic acid triazine) type. A method according to claim 10, characterized characterized in that the components of the mixtures, although arbitrary in beta-sulfato-oxethyl-sulfone form or in vinyl-sulfone form, but that they have the same or very similar adsorption behavior * exhibit. Process according to claims 1 to 22, characterized in that mixtures of two or more color matching or similar reactive dyes of the VS (vinylsulfone) type or VS mixed anchor type in quantity ratios of at least 25% / at most 75% per single dye whereby their individual water solubility due to a diminished number of sulfo groups not fully for a practical use is sufficient. A method according to claim 23, characterized characterized in that the individual dyes (in betasulfato-oxethyl-sulfone form) a water solubility at 50 ° C from 10 to 30 g / l. Process according to claims 1 to 24, characterized in that as nuancing components or for nuancing etchings dyes with the same or with a slightly higher adsorption level * compared to the main component. Process according to claims 1 to 24, characterized in that usually used as salt Na-chloride or Na-sulfate wholly or partly is replaced by the corresponding K salt. A method according to claim 26, characterized characterized in that the reactive dye is a VS (vinylsulfone) or VS / VS dioxazine type in beta-sulfato-oxethyl-sulfone form or in vinyl sulfone form. Process according to claims 26 and 27, characterized in that the reactive dye, the Beta-sulfato-oxethyl-sulfone form or the vinyl-sulfone form of Color Index Reactive Blue 224 represents. A method according to claim 28, characterized characterized in that mixtures of the betasulfato-oxethyl-sulfone form or the vinyl sulfone form of Color Index Reactive Blue 224 with VS (vinylsulfone) / VS double anchor dyes such as Color Index Reactive Black 5 or Blue 203 are used. Process according to claim 2, characterized characterized in that after the addition / addition of the alkali a or more reactive dye (s) of the VS (vinylsulfone) type or a Non-VS type which has a higher physical adsorption level * has / s as the hydrolyzate (s) of the first reactive dye (s), be postponed or added. A method according to claim 30, characterized characterized in that after the addition / addition of reactive dyes, which have an increased physical adsorption level *, additional salt and / or further alkali are added / metered. Process according to claims 1 to 16, characterized in that for combination dyeings Reactive dyes are used, which in a simultaneous Adsorption and fixation test due to a balanced Relation of physical adsorption and chemical reactivity give the same or similar fixing profile **. Process for boiling soaps from reactive dyeings on cellulose fibers (aftertreatment to remove the dye hydrolyzate), characterized in that the physical adsorption level * targeted by adding an adsorption-reducing textile auxiliary is lowered. A method according to claim 33, characterized characterized in that as Adsorptionsverringerndes textile auxiliary a polyvinylpyrrolidone product is used. Process according to claims 33 and 34, characterized in that the adsorption-reducing textile auxiliary in amounts of 0.2 to 5 g / l at a pH between 5 and 9, preferably between 7 and 8 is used.