EP0228639A2 - Process for dyeing wool with reactive dyes - Google Patents

Abstract

The level dyeing of wool with reactive dyes and the simultaneous effort to shorten the dyeing process seem incompatible. According to the invention, it has now been found that, in the course of the pull-out process, metered addition of the acid necessary for fixation over a longer period of time to the dye bath already at the dyeing temperature and not having an acidic fixing agent achieves a reduction in the total treatment time while at the same time ensuring the levelness of the dyeings leaves.

Description

The present invention relates to a process for the level dyeing of wool or the wool portion of fiber mixtures using the pull-dyeing technique in a weakly acidic medium with aqueous liquors of reactive dyes.

The dyeing of wool with reactive dyes is generally known. As a rule, the textile material is treated at pH values between 4 and 6.5 and temperatures between 95 ° and 106 ° C with aqueous solutions of these dyes until the dye bath is exhausted.

This way of dyeing wool is also gaining in importance with the increasing importance of low or non-felt finished wool, because only with reactive dyes can the high authenticity requirements be met, which are placed on articles made from such modified wool, which withstand the tough demands of machine washability (repeated washing at 60 ° C using detergent containing perborate) must withstand without matting.

A problem with dyeing wool with reactive dyes has not yet been completely solved in practice, however, to achieve level dyeings in the course of conventional dyeing measures. Various approaches have already been proposed for this (cf. the German patents DE-C-2 244 089 and DE-C-2 244 240 and the German design specification DE-B-2 244 060), some of which are based on the use of leveling acting aids, but mostly based on special process management, e.g. Adherence to precisely defined pH values, dyeing process taking temperature levels into account or very slow heating of the dye bath containing all ingredients from the start to the end temperature, i.e. Establishing the fixing conditions for dye and fiber material.

A procedure that follows extended heating phases, however, contradicts the currently prevailing trend in dyeing machine construction, which is towards increasingly powerful devices that allow minimal heating up times of only 10 to 15 minutes to set the fixing temperature, because here at the expense of time of poor levelness should be counteracted.

All of the previously mentioned dyeing methods according to the prior art have the prerequisite that reactive dyes and acid (fixing aids) are present from the start next to each other in the pull-out bath that has already been filled with the woolen dye, the actual fixing process occurring under the interaction between the reactive dye and the wool fiber is controlled solely by increasing the liquor temperature.

It was therefore an object of the invention in question to create a pull-out dyeing process for wool or wool components in fiber mixtures with reactive dyes, which, despite the overall treatment times for the dye material previously introduced for dyeing, shortened overall dyeing times with sufficient fastness properties with adequate fastness properties to obtain.

The object set out above is achieved according to the invention in that the reactive dyestuffs and, if appropriate, all other ingredients, but no pull-out liquor containing the acid or acid-donating agents required for fixing the dyestuffs, together with the dyestuff as quickly as possible and in one step to the dyeing temperature in the region heated from 95 ° to 110 ° C, that after reaching the same while maintaining appropriate isothermal conditions for dye fixation, the heated dye bath is then (the) acid - distributed over a longer period of time - and the wool at pH values between 4 and 6.5 colors.

"As soon as possible" in connection with the characteristic of this invention means according to the performance of the dyeing machines used. "In one go" is intended to express that the actual dyeing operation takes place without passing through graduated temperature conditions during the fixing process of the dyes. "Under isothermal conditions" is understood to mean that the temperature of the liquor and the goods is kept constant during the acid addition treatment step and the subsequent dyeing time.

The metering of the acid over a longer period of time to the dye liquor based on fixing conditions for the dye can be carried out quantitatively both linearly and progressively, but the time at which the bath temperature is kept constant in the course of the acid inflow is included in the total dyeing time and consequently, the latter is not extended in accordance with the procedure. The pure dosing time can be from 15 to 60 minutes, with a total dyeing time (including dosing time) from 60 to 90 minutes.

In a linear dosing of the acidic fixing the same quantity of acid is introduced into the dyebath ^p ro unit time. This can be done by introducing the acid, usually diluted with water, either discontinuously in the same portions and at the same time intervals, or by continuously flowing it in the same amount per unit of time.

A progressive dosing of the acidic fixative brings an increasing amount of acid into the dye bath per unit of time as the dosing time progresses, which can also be done manually. Newer dosing devices do this type of dosing automatically, so that only the desired slope of the progression according to a given mathematical function, eg linear, ex ^p o- nentiell or in the manner of a parabolic function, needs to be set.

The amount of acid to be introduced - like the dyeing time - depends on the desired depth of dyeing. As a rule, it is 1 to 5% acetic acid 60 sig, based on the wool weight.

According to the dyeing technique according to this invention, satisfactory dyeing results can be obtained on ordinary, i.e. with non-pretreated wool fibers as well as on chlorinated wool qualities or those that have been made felt-free or low-felt by applying a polyacrylic or polyimine resin film. In this context, wool or appropriately constructed fiber mixtures is understood to mean those in any processing state, that is to say as flakes, sliver, yarn, piece goods or also in the form of finished parts.

For dyeing the wool fibers or the wool portion of fiber mixtures according to the present process, the organic dyes known under this generic term - regardless of the type of their fiber-reactive group - are considered as reactive dyes. This class of dyes is referred to in the Color Index, 3rd edition 1971 and supplements 1975 as "CI. Reactive Dyes" and comprises chemical compounds with dye character which are able to form a covalent bond with OH groups and / or NH group-containing fibers . These are predominantly those dyes which contain at least one group which is reactive with hydroxyl or amino groups in the fiber material having a polyamide structure, a precursor therefor or a substituent which is reactive with the above-mentioned constituents of the fiber molecule. As the basic body of the chromophoric Sy-. Stems of these organic dyes are particularly suitable those from the series of the azo, anthraquinone and phthalocyanine compounds, it being possible for the azo and phthalocyanine dyes to be both metal-free and metal-containing. Reactive groups and precursors which form such reactive groups include, for example, epoxy groups, the ethyleneimide group, the vinyl grouping in the vinylsulfone or acrylic acid radical, also the β-sulfatoethylsulfone group, the β-chloroethylsulfone group or the β-dialkylamino-ethylsulfone group. Derivatives of the tetrafluorocyclobutyl series, for example tetrafluorocyclobutyl acrylic acid, are also suitable for this process. The reactive substituents in reactive dyes are those that are easily removable and leave an electrophilic residue. In this regard, 1 to 3 halogen atoms on the following ring systems are of interest as substituents: quinoxaline, triazine, pyrimidine, phthalazine, pyridazine and pyridazone. Dyes with several identical or different reactive groups can also be used. Such reactive dyes of the type defined above often have more than one sulfonic acid group (except in the reactive grouping of the dye) in the molecule, which can be distributed as desired over the chromophore, but are preferably bound to its aromatic radicals.

For carrying out the present invention, preference is given to using vinylsulfone-type dyes with which the fiber reacts via an addition mechanism via the vinylsulfone form of the dye. Also useful as coloring substances in the claimed process are the conversion products of such known sulfonyl reactive dyes with e.g. Methyl taurine in which the reactive group is temporarily masked.

• Man setzt das wäßrige Färbebad mit allen Zutaten, wie Farbstoff, Hilfsmittel und eventuelle Chemikalien, außer der benötigten Säure, an und treibt es zusammen mit dem Farbgut, so rasch wie es die maschinelle Einrichtung zuläßt, auf die vom Fasermaterial abhängige Färbetemperatur. Hierbei wird bereits im Zuge der Aufheizphase gegenüber den herkömmlichen Arbeitsweisen ein Zeitgewinn von 10 bis 30 Minuten erzielt. Sofort nach Erreichen dieser Färbetemperatur wird mit dem dosierten Zusatz der erforderlichen Säure begonnen. Er kann portionsweise nach einem bestimmten Zeitschema, wie z.B. in dem nachfolgenden Beispiel 1, oder kontinuierlich nach einer vorgegebenen mathematischen Funktion (linear oder z.B. exponentiell oder in der Art einer Parabelfunktion) mit einem Dosiergerät erfolgen, beispielsweise nach dem Prinzip, wie es in der europäischen Offenlegungsschrift EP-A2-0 126 042 erläutert wird. Geräte dieses Typs befinden sich seit neuerer Zeit im Handel.

The procedure itself is basically carried out as follows, with the type of dosage being a large variation width can be granted, as can already be seen from the dosing times mentioned. In general, the acid is added diluted, which allows a better dosage gradation:

• The aqueous dyebath is prepared with all the ingredients, such as dye, auxiliary agents and any chemicals, except for the acid required, and is driven together with the dyestuff, as quickly as the machine allows, to the dyeing temperature which is dependent on the fiber material. In the course of the heating-up phase, a time saving of 10 to 30 minutes is achieved compared to conventional working methods. Immediately after reaching this dyeing temperature, the metered addition of the required acid is started. It can be carried out in portions according to a certain time schedule, such as in Example 1 below, or continuously according to a predetermined mathematical function (linear or, for example, exponential or in the manner of a parabolic function) with a dosing device, for example according to the principle described in European Published patent application EP-A2-0 126 042. Devices of this type have been on the market recently.

The bath temperature is kept constant during the acid addition and for a certain time afterwards. After the intended dyeing time, the dyeing is finished as usual for wool.

The following examples are not intended to restrict the claimed process in any way, especially not with regard to the reactive dyes used, but merely serve to illustrate the procedure according to the present invention. The percentages contained in these exemplary embodiments relate to the weight of the objects designated in this way and, in the case of wool, are calculated on the dry state of the color material. The The reactive dyes mentioned are used in a commercially available form and quality.

Dyes, which are conversion products of sulfonyl reactive dyes with N-methyl taurine, are present in the structure represented by the respective formula after being dissolved correctly.

example 1

• 3 % des Reaktivfarbstoffes der Formel
  
• 1 % eines durch Umwandlung aus dem entsprechenden Farbstoff vom Vinylsulfon-Typ mit N-Methyltaurin erhaltenen Reaktivfarbstoffes der Formel
  
• 1,5 % eines Hilfsmittelgemisches aus dem Umsetzungsprodukt von 1 Mol Stearylamin mit 12 Mol Ethylenoxid,versetzt mit Triisobutylphosphat als Entschäumer, und
• 2 % Ammoniumacetat.

To dye 80 kg of a wool knitted fabric finished with a polyimine resin without felt using the pull-out technique at a liquor ratio of 1:10, an aqueous bath of 40 ° C. with the following ingredients is prepared in a dyeing machine:

• 3% of the reactive dye of the formula
  
• 1% of a reactive dye of the formula obtained by conversion from the corresponding dye of the vinyl sulfone type with N-methyl taurine
  
• 1.5% of an auxiliary mixture from the reaction product of 1 mol of stearylamine with 12 mol of ethylene oxide, mixed with triisobutyl phosphate as a defoamer, and
• 2% ammonium acetate.

The addition of acid is initially avoided. Under these conditions, the bath has a pH of 6.8.

Während dieser Maßnahme wird die Temperatur des Bades konstant bei 100°C gehalten. Die eingebrachte Säure ist deshalb vorgängig auf etwa Färbetemperatur vorgewärmt worden.The bath loaded with the dye is now brought to circulation and heated to the dyeing temperature of 100 ° C. within 10 minutes. Immediately after reaching this temperature, the total addition is started
4 4 acetic acid (60%), which corresponds to a liquid volume of 3.2 1. This dosing should be carried out in portions, but progressively, in equal quantities. To this end, the acid is diluted to a volume of 15 l using water and the following amounts of this solution are added after every 7 minutes in accordance with the staggering given below:

During this measure, the temperature of the bath is kept constant at 100 ° C. The acid introduced has therefore been preheated to about the dyeing temperature.

After the addition of acid, which has led to a pH of the bath of 4.7, is finished, the goods are further dyed for a further 30 minutes at the same temperature. Then the extracted liquor, including the dyed wool, is cooled, the latter rinsed with water and finished as usual.

A brilliant red dyeing of the knitted fabric with good wet fastness properties is obtained. Contrary to expectations, the levelness of the coloring is very good.

Example 2

• Dazu wird das Farbgut in eine wäßrige Flotte von 40°C eingebracht, die als Bestandteile
  • 3 % des Farbstoffes Reactive Blue 19 mit der C.I.-Nr. 61200,
  • 1 % des Reaktivfarbstoffes der Formel
    
  • 1,5 % des Hilfsmittelgemisches gemäß Beispiel 1, und
  • 1 % Ammoniumacetat

enthält, worauf man dieses Färbebad in Zirkulation versetzt und es innerhalb von 10 Minuten auf die Färbetemperatur von 100°C erhitzt. Dann werden der unter Fixierbedingungen befindlichen Flotte über ein Dosiergerät von Typ ADC 100 der Firma ADCON AB, Boras/Schweden
2,4 1 Essigsäure (60 %ig),
mittels Wasser auf ein Volumen von 20 1 verdünnt, kontinuierlich sowie bei Einhaltung einer pro Zeiteinheit mengenmäßig 50 %igen Progression während eines Zeitraumes von 45 Minuten zugesetzt.60 kg of a ready-to-dye fabric made of wool that has not been pretreated with an anti-felt finish are dyed in a tree dyeing machine by pulling out at a liquor ratio of 1:15 as follows:

• For this purpose, the dyestuff is introduced into an aqueous liquor of 40 ° C., which are used as components
  • 3% of the dye Reactive Blue 19 with the CI no. 61200,
  • 1% of the reactive dye of the formula
    
  • 1.5% of the auxiliary mixture according to Example 1, and
  • 1% ammonium acetate

contains, whereupon this dye bath is circulated and heated to the dyeing temperature of 100 ° C. within 10 minutes. Then the fleet under fixation conditions is fed via a metering device of type ADC 100 from ADCON AB, Boras / Sweden
2.4 1 acetic acid (60%),
diluted to a volume of 20 l with water, added continuously and with a 50% progression per unit of time over a period of 45 minutes.

After a further 20 minutes of dyeing at 100 ° C, the dyeing is complete. Then you cool down the fleet and goods, rinses the latter with water and finishes the dyed wool as usual.

A very level blue dyeing of the wool fabric with good fastness properties is obtained.

Example 3

• Für diese Aufgabe wird ein wäßriges Färbebad von 60°C mit
  • 5 % des Farbstoffes Reactive Black 5 mit der C.I.-Nr. 20505,
  • 0,5 % des Reaktivfarbstoffes der Formel
    
  • 0,5 % des Reaktivfarbstoffes mit der Formel
    
  • 1 % des Hilfsmittelgemisches gemäß Beispiel 1, und
  • 2 % Ammoniumacetat

beschickt und zusammen mit der eingebrachten Ware im Verlauf von 15 Minuten auf die Färbetemperatur von 106°C aufgeheizt. Dann beginnt man manuell mit der Säuredosierung, portionsweise in linearen Mengen nach jeweils gleichen Zeitabständen, in die unter Fixierbedingungen stehende Flotte. Dazu werden
5, 2 1 Essigsäure (60 %ig),
mittels Wasser auf ein Volumen von 10 1 verdünnt und von dieser Lösung, welche man zweckmäßig vorwärmt, wird alle 3 Minuten jeweils 1 1 dem Bad zugegeben. Nach dem letzten Säurezusatz färbt man die Ware noch weitere 20 Minuten bei der angegebenen Temperatur, und kühlt Bad samt Farbgut dann ab, spült die gefärbte Wolle mit Wasser und stellt diese wie üblich fertig.120 kg of a wool yarn that is not finished with a felt-free finish are opened on X-bobbins by dyeing at a liquor ratio of 1:15 to dye them real black:

• For this task, an aqueous dye bath of 60 ° C is used
  • 5% of the dye Reactive Black 5 with the CI no. 20505,
  • 0.5% of the reactive dye of the formula
    
  • 0.5% of the reactive dye with the formula
    
  • 1% of the auxiliary mixture according to Example 1, and
  • 2% ammonium acetate

loaded and heated together with the goods brought to the dyeing temperature of 106 ° C over 15 minutes. Then you start the acid dose manually tion, in portions in linear amounts after the same time intervals, into the liquor under fixation conditions. To do this
5, 2 1 acetic acid (60%),
diluted to a volume of 10 l with water and 1 l of this solution, which is appropriately preheated, is added to the bath every 3 minutes. After the last addition of acid, the goods are dyed for a further 20 minutes at the specified temperature, and then the bath and dye are cooled, the dyed wool is rinsed with water and finished as usual.

The desired real and level black dyeing of the yarn is obtained.

Example 4

200 kg of a wool comb finished with a polyacrylic resin film to be felt-free must be dyed in the packing system by pulling out at a liquor ratio of 1: 8.

• 0,5 % eines durch Umwandlung aus dem entsprechenden Farbstoff vom Vinylsulfon-Typ mit N-Methyltaurin erhaltenen Reaktivfarbstoffes der Formel
  
• 0,5 % eines durch Umwandlung aus dem entsprechenden Farbstoff vom Vinylsulfon-Typ mit N-Methyltaurin erhaltenen Reaktivfarbstoffes der Formel
  
• 0,5 % eines durch Umwandlung aus dem entsprechenden Farbstoff vom Vinylsulfon-Typ mit N-Methyltaurin erhaltenen Reaktivfarbstoffes der Formel
  
• 1,5 % des Hilfsmittelgemisches gemäß Beispiel 1, und
• 2 % Ammoniumacetat,

heizt das Bad innerhalb von 15 Minuten auf die Färbetemperatur von 106°C auf und beginnt sofort mit der kontinuierlichen, programmgesteuerten Säuredosierung mit der Maßgabe, daß unter den genannten Temperaturbedingungen zu dieser Flotte
3 1 Essigsäure (60 %ig),
mit Wasser auf ein Volumen von 30 1 verdünnt, bei Einhaltung einer pro Zeiteinheit mengenmäßig 60 %igen Progression während einer Zeitdauer von 45 Minuten zugesetzt werden.For this purpose, an aqueous liquor at 40 ° C. is charged with

• 0.5% of a reactive dye of the formula obtained by conversion from the corresponding dye of the vinyl sulfone type with N-methyl taurine
  
• 0.5% of a reactive dye of the formula obtained by conversion from the corresponding dye of the vinyl sulfone type with N-methyl taurine
  
• 0.5% of a reactive dye of the formula obtained by conversion from the corresponding dye of the vinyl sulfone type with N-methyl taurine
  
• 1.5% of the auxiliary mixture according to Example 1, and
• 2% ammonium acetate,

heats the bath to the dyeing temperature of 106 ° C within 15 minutes and immediately begins with the continuous, program-controlled acid metering with the proviso that under the temperature conditions mentioned to this liquor
3 1 acetic acid (60%),
diluted with water to a volume of 30 1, if a 60% progression per unit time is observed, be added over a period of 45 minutes.

After the metering is complete, the goods are further dyed at 106 ° C. for 10 minutes, then cooled together with the liquor, rinsed with water and finished as usual for wool.

You get a very smooth brown ridge.

Claims (9)

1. A process for the level dyeing of wool or the wool content of fiber mixtures using the exhaust dyeing technique in a weakly acidic medium with aqueous liquors of reactive dyes, characterized in that the dyes and any other ingredients, but no acid required for fixing the dyes or pulling-out liquor containing acid-releasing agents together with the dyestuff as quickly as possible and heated to the dyeing temperature in the range from 95 ^* to 110 ° C. in such a way that after the same has been reached while maintaining appropriate isothermal conditions for dye fixation, the heated dyebath then add acid over a longer period of time and dye the wool at pH values between 4 and 6.5. 2. The method according to claim 1, characterized in that the addition of the entire acid is carried out discontinuously in equal proportions after the same time intervals. 3. The method according to claim 1, characterized in that the addition of the entire acid is carried out continuously in the same amount per unit of time. 4. The method according to claim 1, characterized in that the addition of the entire acid is carried out discontinuously in increasing proportions after the same time intervals. 5. The method according to claim 1, characterized in that the addition of all the acid in continuously increase gender quantity is carried out according to a certain time schedule according to a mathematical function. 6. The method according to one or more of claims 1 to 5, characterized in that the addition of the total acid is carried out within a period of 15 to 60 minutes. 7. The method according to one or more of claims 1 to 6, characterized in that the treatment time of the wool at dyeing temperature is a total of between 60 and 90 minutes. 8. The method according to one or more of claims 1 to 7, characterized gekennzeichent that one dyes non-pretreated wool with an anti-felt finish. 9. The method according to one or more of claims 1 to 7, characterized in that pretreated by chlorination, or provided with a pad made of a polyimine resin or a polyacrylic resin, low-felt or felt-free finished wool.