EP0081134B1 - Method of applying a fixating liquid to textile web materials printed or dyed with reactive dyes - Google Patents

Description

The present invention relates to a process for the continuous application of alkaline fixing liquors to unfixed textile fabrics made of cellulose fibers or their mixtures with polyester fibers, previously treated with reactive dyes without adding alkali and optionally dried, by spraying by means of rotating liquid spray heads onto the uniformly passing fiber material in a coherent manner with the printed or block dyed Thin layer covering surfaces.

In practice, printing and block dyeing with reactive dyes on fabrics made of cellulose fibers is carried out in practice according to a one- or two-stage procedure. All two-stage methods with this orientation have in common that the printing ink or pad liquor is prepared without alkali; It is only in the second step, that is to say in a second phase, that an alkali solution must be applied to the goods which have been printed or padded under neutral conditions and which may have dried, which is necessary for the subsequent fixing of the dye on the fiber. As a rule, the application of this chemical solution takes place on a padder with two or more rollers, the treated textile material absorbing 60 to 100% (based on the weight of the dry fiber material) of the fixing liquor. During the actual fixation operation, the tissue is subjected to heat; this step can also be done in certain cases by standing at room temperature for a long time.

In recent years, a large number of so-called minimal application processes for treatment fluids have been developed, all of which aim to reduce the amount of liquor applied to the textile goods. In such a project, you receive the most even order possible, including in that the preparation in question is sprayed or foamed onto the web in finely divided form.

All spray processes are therefore primarily based on the idea of economical use of chemicals compared to other methods in this field.

As far as the known measures in the field of spray technology are concerned, mechanical spraying is carried out either with compressed air-controlled nozzles (DE-OS 22 49 330) or with high-rotation liquid spray heads (FR-PS 22 51 651). The latter generally operate at 30,000 to 50,000 revolutions per minute (rpm).

However, the finer such a spray mist is, the more uniform is the application of the treatment agent - provided that no deflection of the mist is caused. The droplet clouds are, however, already influenced by relatively weak air currents and then deviate from the path largely predetermined by the spray characteristics of the nozzle. As a result, an undesirable, sometimes unevenly thick application of the preparation over the textile web occurs. Of course, this phenomenon also contributes to a certain burden on the environmental conditions.

To switch off such a drift and to even out the spray pattern, attempts have therefore already been made according to DE-OS 24 06 831 and also according to FR-PS 22 51 651 to carry out the spraying process in an electrostatic voltage field.

For this purpose, a high voltage is applied to the atomizing device, on the one hand, and to the metallic base over which the textile goods are guided, on the other hand, so that the field of tension spreads perpendicularly with respect to the textile web and the resulting fine liquid droplets receive a positive or negative charge. These are then pulled onto the web by electrostatic forces along the electrical field lines. However, the use of strong electrical fields requires special safety measures; it must be completely ruled out if flammable liquids are to be applied.

Another concept for the fleet order on the web, which is largely independent of the statistical fluctuations in the ambient air that otherwise occur, is according to DE-OS 25 43 524 to distribute the spray evenly over the entire width of the goods by means of a suction process. As a result of a laminar air flow, which runs in the direction of the nozzle jets, the atomized droplets are given a safe guidance, as a result of which a forced flow of the spray mist and the circulating air through the material web is achieved. In this way, in addition to the regular distribution of the droplets on the material surface, a depth effect is also achieved. According to a further development for improving the eye-spraying technique in Gesamtzusammenhan ^g with the fleet minimum application in accordance with DE-OS 29 32 124 is carried out by spraying a high-rotation-liquid spray; the sprayed liquid is additionally directed onto the material web by an air flow directed laterally onto the spray cone.

However, high-rotation liquid spray heads and nozzles controlled by compressed air are only suitable for spraying low-viscosity preparations. One therefore works according to this conventional spraying method, for example predominantly with aqueous solutions of sodium carbonate or sodium hydroxide solution. For textile webs of 160 cm width, 1 to 3 spray heads must be used.

In addition, all previously available minimal application methods for treatment fleets, including the previously explained designs, failed due to the poor controllability at variable speeds and / or the high investment costs for the system.

Knowing the shortcomings of the spraying methods known from the relevant literature, the task for the present invention was to modify the conventional methods in this field in accordance with the needs of practice and also to make them accessible for the use of more viscous solutions of treatment agents to be sprayed . In particular, ways and means should be found which, while retaining the positive effects of the working method, allow spraying fixatives to be sprayed at variable speeds on a technically simple and inexpensive system.

It has now been found that, as liquid preparations of alkaline fixing agents, even minimal amounts of highly viscous solutions can be sprayed uniformly onto textile webs when the number of revolutions of rotating liquid spray heads from 30,000 to 50,000 rpm to about 5,000 rpm is reduced.

The object of the invention is thus achieved in that the fixing liquors are more viscous solutions based on soda water glasses, which have a degree of 37-50 ° Be or a specific weight of 1.34 to 1.53, optionally in a mixture with other alkalis , are sprayed onto the textile material by means of rotors which operate at a speed of 3,000 to 7,000 rpm, preferably 5,000 rpm, and have a spray width of 5 to 20 cm, preferably 10 cm, per rotor.

In addition to a reduction in the number of revolutions of the rotating liquid spray head, the spray width of a rotor is thus also substantially smaller than that of a high-rotation liquid spray head. In accordance with the width of the textile goods, the necessary number of rotors is arranged side by side in the rotor carrier. In order to achieve better wetting of densely packed or heavier product qualities, the rotor carriers can be installed on both sides of the running textile web in the treatment room. In this way, the same result is obtained, which is achieved with far more complex apparatus precautions according to the forced flow of the spray mist described in DE-OS 29 32 124 by suction through the web.

The process according to the invention can be used with particular advantage for applying minimal amounts of fixing agents containing alkaline substances to prints and block dyeings with reactive dyes, surprisingly also with block dyeings and with textiles printed with large patterns, despite the high amounts of thickener applied and the associated bonding and narrowing the stitches absorb the fixing chemicals sufficiently quickly. The liquid applied is largely absorbed by the fabric or the thickener film of the printing ink.

According to FR-A-1 525 578, it is already known to spray a highly concentrated glue solution onto textiles by means of rotors which work at a speed of 3,000 to 5,000 rpm. A transfer of this conventional procedure to unfixed prints and dyeings, however, cannot easily be realized because the water-soluble reactive dyes run out and smear the white background. It is only when a suitable fixing liquor based on soda water glasses has been developed that it is possible to precisely fix sharp contours on white surfaces.

Known, continuous or discontinuous techniques can be used to fix the reactive dyes applied to the textile web in a two-phase procedure, together with the required fixing alkali, such as the steaming process, flash steaming process, infrared process or cold residence process.

For the application of fixative by spraying according to the present invention, the highly viscous solutions which come into consideration are the sodium water glasses which are widespread in the textile industry. They are defined by a degree of 37-50 ° Be, which corresponds to a specific weight of 1.34 to 1.53. Depending on the fixing time required for the type of dye (5 seconds to 24 hours), they are used either alone or in a mixture with other alkalis, preferably sodium hydroxide solution, and water.

The amount of the sprayed solution depends on its concentration, on the throughput speed of the textile material and on the concentration and amount of the printed or padded dye. In the case of more concentrated solutions of the fixing agent, the throughput speed can be increased, just as the sprayed amount is increased.

• - S0₂-CH₂-CH₂-Hal (I)
• - S0₂-CH₂-CH₂-0-S0₃X (11)
• - NH-S0₂-CH₂-CH₂-0-S0₃X (111)
• - S02-CH=CHy (IV)
• enthalten, worin X Wasserstoff oder ein

Metallkation und Hal Halogen bedeuten.According to the process, the reactive dyes for short fixing times are predominantly those which contain reactive radicals of the formulas I-IV

• - S0 ₂ -CH ₂ -CH ₂ -Hal (I)
• - S0 ₂ -CH ₂ -CH ₂ -0-S0 ₃ X (11)
• - NH-S0 ₂ -CH ₂ -CH ₂ -0-S0 ₃ X (111)
• - S02-CH = CHy (IV)
• contain, wherein X is hydrogen or a

Metal cation and Hal mean halogen.

For longer fixation times (6 minutes to 24 hours), find in addition to those listed previously Products also use dyes which have as a reactive group the chloraminotriazine, dichloropyrimidine, trichloropyrimidine, dichlorotriazine, monochlorotriazine, quaternized chlorotriazine or the dichloropyridazine group.

The present invention is suitable for the fixation of reactive dyes on sheet-like cellulose fiber materials of all types of processing, such as woven, knitted or non-woven fabrics. It enables an order of 15 to 40 percent by weight of the fixative fleet, based on the dry goods. Higher application quantities, which can result, for example, from the overlapping of the spray compartments of two adjacent rotors, have no effect on the sharp state of the prints and the degree of fixation of the dyes in this process. This is a great advantage compared to spraying with aqueous solutions of sodium carbonate, sodium hydrogen carbonate or sodium hydroxide solution.

The following examples serve to illustrate the invention. The percentages given therein are percentages by weight and, in the case of the data for the liquor intake, are based on the weight of the dry goods. The water glasses according to the examples are each soda water glass.

example 1

• 60 g of the dye Reactive Violet 5 (C.I. No. 18 097) are in
• Dissolve 430 g of hot water and the solution is in
• 500 g of a 4% aqueous alginate thickener was stirred in. Then you put in this print paste preparation
• Add 10 g sodium 3-nitrobenzenesulfonic acid.

• 600 ml Wasserglas von 40° Be
• 200 ml Natronlauge von 50° Be und
• 200 ml kaltem Wasser

besteht. Zur Farbstoff-Fixierung dämpft man das Textilgut 5 Sekunden in einem Blitzdämpfer; die erzeugte Druckfärbung wird danach wie üblich nachbehandelt und getrocknet.With this printing paste, a mercerized cotton fabric is printed in rouleaux printing and dried. The running web is then sprayed with a solution using a liquid spray head that rotates at approx. 5,000 revolutions per minute (rpm) with a liquor absorption of 30%

• 600 ml water glass of 40 ° Be
• 200 ml sodium hydroxide solution at 50 ° Be and
• 200 ml of cold water

consists. To fix the dye, dampen the textile material in a flash damper for 5 seconds; the printing stain is then post-treated and dried as usual.

A violet print with good fastness properties is obtained.

Example 2

• 30 g of the dye reactive yellow 129 are with
• 458 g of hot water dissolved and this solution is then in
• 500 g of a 4% aqueous alginate thickener were stirred in. Then you give the printing paste approach
• 2 g monosodium phosphate and
• Add 10 g sodium 3-nitrobenzenesulfonic acid.

• 600 ml Wasserglas von 40° Be und
• 400 ml Natronlauge von 50° Be

besteht. Nach einem kurzen Luftgang wird die Textilbahn nunmehr auf einer kontinuierlich laufenden Transporteinrichtung abgelegt, wo man sie zwecks Farbstoff-Fixierung mindestens 15 Minuten bei Raumtemperatur verweilen läßt. Abschließend wird das so bedruckte Gewebe wie üblich nachbehandelt und getrocknet.This printing paste is used to print and dry a leached fabric made from regenerated cellulose fibers using flat film printing. The goods are then sprayed as in Example 1 with a liquor absorption of 35% with a solution which consists of

• 600 ml water glass of 40 ° Be and
• 400 ml sodium hydroxide solution at 50 ° Be

consists. After a short air passage, the textile web is now placed on a continuously running transport device, where it is left to remain at room temperature for at least 15 minutes for the purpose of dye fixation. Finally, the fabric printed in this way is post-treated and dried as usual.

A yellow print with good fastness properties is obtained.

Example 3

• 80 g of the dye Reactive Black 5 (C.I. No. 20 505) are mixed with
• Dissolved 408 g of hot water and this solution is now in
• 500 g of a 4% aqueous alginate thickener were stirred in. Then you give the print paste preparation
• 2 g monosodium phosphate and
• Add 10 g sodium 3-nitrobenzenesulfonic acid.

• 950 ml Wasserglas von 38° Be und
• 50 g Ätznatron

besteht. Nach einem kurzen Luftgang wird die Ware abgetafelt, mit einer Plastikfolie abgedeckt und 24 Stunden bei Raumtemperatur liegengelassen, während der die Fixierung des Reaktivfarbstoffes bewirkt wird. Zur Fertigstellung der Druckfärbung wird das Textilgut sodann wie üblich nachbehandelt und getrocknet.This printing paste is used to print and dry a fabric made of mercerized cotton in rouleaux printing. The goods are then sprayed as in Example 1 with a liquor absorption of 35% with a solution which consists of

• 950 ml water glass of 38 ° Be and
• 50 g caustic soda

consists. After a short breath of air, the goods are removed from the table, covered with a plastic film and left to stand at room temperature for 24 hours, during which the reactive dye is fixed. To complete the printing dyeing, the textile material is then post-treated and dried as usual.

A black print with good fastness properties is obtained.

Example 4

• 60 g of the reactive red 58 dye are included
• 440 g of hot water is dissolved and this solution is then in
• 500 g of a 4% strength aqueous alginate thickener which already contains 20 g of 3-nitrobenzenesulfonic acid sodium.

• 500 ml Wasserglas von 38° Be,
• 400 ml Wasser und
• 100 g Natriumbicarbonat

besteht. Zur Farbstoff-Fixierung wird das Textilgut anschließend 8 Minuten in einem Hängeschleifendämpfer mit Sattdampf gedämpft und wie danach üblich nachbehandelt und getrocknet.This printing paste is used to print and dry a leached fabric made from regenerated cellulose fibers in Rouleaux printing. The continuously running material web is now sprayed with a solution as in Example 1 with a liquor absorption of 20%

• 500 ml water glass of 38 ° Be,
• 400 ml of water and
• 100 g sodium bicarbonate

consists. To fix the dye, the textile is then steamed with saturated steam in a hanging loop steamer for 8 minutes and then treated and dried as usual.

A red print with good fastness properties is obtained.

Example 5

• 60 g of the dye Reactive Orange 12 are included
• 440 g of hot water is dissolved and this solution is then in
• 500 g of a 4% aqueous alginate thickener which already contains 20 g of 3-nitrobenzenesulfonic acid sodium are stirred in.

• 60 g Natriumcarbonat,
• 640 ml Wasser und
• 300 ml Wasserglas von 38° Be

besteht. Das bedruckte Textilgut wird nun zwecks Fixierung des Reaktivfarbstoffes 6 Minuten in einem Hängeschleifendämpfer mit Sattdampf gedämpft und abschließend wie üblich nachbehandelt.This printing paste is used to print and dry knitted fabric made from regenerated cellulose fibers in Rouleaux printing. Then the web is sprayed with a solution according to the instructions of Example 1 with a liquor absorption of 20%, which consists of

• 60 g sodium carbonate,
• 640 ml of water and
• 300 ml water glass of 38 ° Be

consists. The printed textile material is then steamed for 6 minutes in a hanging loop damper with saturated steam for the purpose of fixing the reactive dye and then aftertreated as usual.

An orange print with good fastness properties is obtained.

Example 6

• Eine Mischung aus
  • 40 g des nichtionisch formierten Farbstoffes Disperse Red 54:1 und
  • 40 g der flüssigen Handelsform des Farbstoffes Reactive Orange 16 (C.I. Nr. 17 757) wird zunächst in
  • 70 g Wasser von 80-90 °C dispergiert bzw. gelöst und sodann mit
  • 150 g kaltem Wasser verdünnt. Dieser Farbstoffansatz wird nun in
  • 700 g einer Verdickung eingerührt, die aus einer Mischung aus 60 % einer 3 %igen, wäßrigen Lösung eines Ammoniumpolyacrylats vom Molgewicht 0.6.106 und 40 % einer 2 obigen, wäßrigen Lösung eines Co-polymerisats aus Propylen und Maleinsäure-anhydrid (Molverhältnis 1:1) vom Molgewicht 1,5. 10⁶ besteht.

A mixed fabric made of polyester fiber / rayon (85:15) is printed in rouleaux with a printing paste which is produced as follows:

• A mix of
  • 40 g of the nonionically formed dye Disperse Red 54: 1 and
  • 40 g of the liquid commercial form of the dye Reactive Orange 16 (CI No. 17 757) is initially in
  • 70 g of water at 80-90 ° C dispersed or dissolved and then with
  • Diluted 150 g of cold water. This dye approach is now in
  • 700 g of a thickener stirred in, which consists of a mixture of 60% of a 3% aqueous solution of an ammonium polyacrylate with a molecular weight of 0.6.106 and 40% of a 2 above aqueous solution of a copolymer of propylene and maleic anhydride (molar ratio 1: 1) with a molecular weight of 1.5. 10 ⁶ exists.

After the fabric printed in this way has dried, the disperse dye is first fixed to the polyester portion of the fiber mixture by treatment in a hanging loop damper with superheated steam for 7 minutes at 175 ° C. Then the textile material for fixing the reactive dye on the cellulose component, as indicated in Example 2, is sprayed and finished.

An orange print with good fastness properties is obtained.

Example 7

• 30 g of the dye Disperse Blue 56 (C.I. No. 63 285) are sprinkled in
• Well dispersed 270 g of water at 40-50 ° C using a high-speed stirrer. Be separate from it
• 30 g of Reactive Blue 19 dye (C.I. No. 61 200) in
• 270 g of boiling water dissolved. Both approaches are then in
• 400 g of cold water entered, which contains 4 g / I of a wetting agent and 20 g / I of an anti-migration agent. The liquor thus prepared is finally adjusted to a pH of 5-6 using acetic acid.

With this liquor, a blended fabric made of polyester fiber / cotton (50:50) with a liquor absorption of 60% is padded and dried. The disperse dye is then fixed to the polyester component for 60 seconds by thermosoling on the stenter using hot air at 200 ° C.

• 200 ml Wasserglas von 38° Be
• 60 ml Natronlauge von 38° Be
• 740 ml Wasser

besteht. Anschließend wird die Gewebebahn aufgedockt, in Plastikfolie eingeschlagen und 8 Stunden bei Raumtemperatur gelagert, in deren Verlauf der Reaktivfarbstoff auf dem Baumwollanteil des Textilgutes fixiert. Zur Fertigstellung wird die Färbung danach wie üblich nachbehandelt und getrocknet.The cooled goods are now sprayed with a solution according to the instructions of Example 1 with a liquor absorption of 30%

• 200 ml water glass of 38 ° Be
• 60 ml sodium hydroxide solution at 38 ° Be
• 740 ml of water

consists. The fabric web is then docked, wrapped in plastic film and stored for 8 hours at room temperature, in the course of which the reactive dye on the Cotton portion of the textile goods fixed. The dyeing is then treated and dried as usual afterwards.

A blue color is obtained on both fiber components with good fastness properties.

Claims (4)

1 .Process for the continous application of alcaline fixing liquors on unfixed, previously with reactive dyestuffs without addition of alcali treated and eventually dryed textile webs made of cellulosic fibres or their mixtures with polyester fibers, by means of atomizing with rotating spraying nozzles on the passing textile webs in a uniform layer covering the printed or pad dyed areas, fixing liquors of higher viscosity, based on solutions of sodium silicate with a density of 37 to 50° Be identical with a specific gravity of 1,34 to 1,53 by means of rotating nozzles with 3000 to 7000 revolutions per minute and a spraying width of 5 to 20 cm per rotating nozzle.

2. Process according to Claim 1, in which the solutions of higher viscosity, based on sodium silicate are sprayed in mixture with other alcalis.

3. Process according to Claim 2, in which the solutions of higher viscosity, based on sodium silicate, are sprayed in mixture with other alcalis with addition of water.

4. Process according to Claims 1 to 3, in which the sprayed prints or pad dyeings are fixed according the strength of the alcalis added to the sodium silicates and the mixture with water in a period of 5 seconds up to 24 hours.