EP0186814A1 - Method for fixing reactive dyes in steamers for fabrics in a festooned form - Google Patents

Abstract

Prints and pad-dyeings with reactive dyes which, for example owing to their molecular size, require a long fixing time on cellulose fibre material cannot be fixed to the full depth shade by the conventional two-phase steaming process. The hitherto unknown combination of minimum add-on systems by means of rolls or draw bars for the fixing alkali and fixing the dyes in a festoon ager eliminates the existing defects.

Description

The present invention relates to the continuous fixation of prints and block dyeing with reactive dyes on textile webs of cellulose fibers or their blends with synthetic fibers, preferably with polyester fibers, according to a two-phase steaming technique, the dissolved alkaline fixing agent in the form of minimal liquor quantities on the unfixed , is previously applied with the reactive dyes without alkali added or block-dyed and optionally dried fiber material.

The fixation of prints or 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 of this type have in common that the printing paste or pad liquor containing the dye is prepared without the addition of alkali and thus acts on the textile material. Only in a second operation is an alkali solution then applied to the goods printed or padded under neutral or weakly acidic conditions, which may be intermediate dried, which is required for the subsequent fixing of the dye on the fiber. As a rule, this chemical solution is applied on a padder with two or more rollers, the pretreated textile material absorbing 60-100% (based on the weight of the dry fiber material) of the fixing liquor. Instead of a foulard, a minimal application unit can also be used for treatment with the fixative. During the actual fixing operation due to the action of heat in the special two-phase dampers previously used, the goods are then briefly steamed at 110-140 ° C for 5-30 seconds.

Sodium hydroxide solution of 32.5% (38 ° Be) in a concentration of 70-120 ml per liter of padding liquor is mainly used as an alkaline agent for fixing the reactive dyes in the second treatment stage in the previously known two-phase padding steaming process. Water glass of 38 ° Be in amounts of 50-100 ml / 1 is only added to this fixing liquor to increase the viscosity thereof and to achieve a uniform film on the fixing alkali on the application rollers.

The high amounts of 70-120 ml / 1 sodium hydroxide solution of 32.5% (38 ° Be) according to this prior art are necessary because some reactive dyes - mainly the turquoise brands with a large dye molecule - are relatively slow with the OH groups of the Cellulose react. On mercerized cotton you can achieve flawless results and a good color yield, on non-leached cellulose and modified regenerated fibers, however, you cannot achieve deep turquoise tones under these conditions. This is an important reason why the two-phase pad steaming process has generally not been widely used in the case of reactive dyes. Doubling the steaming time would result in a better fixation of the turquoise marks, but is not an option because the equipment requirements are not met and at the same time the other colors are damaged by the high amounts of caustic soda.

Knowing the inadequacies of the fixing processes for reactive dyes known from the relevant literature, the task for the present invention was now to modify the conventional methods in this field in accordance with the needs of practice and also for the use of cellulose fiber to make inert reactive dyes accessible. In particular, ways and means should be developed which put an end to the long-term search for a quick-fixing reactive turquoise and which, while maintaining the positive effects of the working method, allow so-called quick-fixers in addition to those that react slowly in the case of printing and block dyeing with mixtures of reactive dyes To use dyes of this type and to enable stable pressure drops even with strong fluctuations in the steaming time.

It has now surprisingly been found that, particularly on non-leached cellulose fibers, substantially better color yields are obtained on the applied reactive dyes if, for the purpose of fixing the same, instead of a special two-phase system of conventional construction principle, the hanging loop dampers widely used in textile printers for the single-phase mode of operation are used.

The object of the invention is thus achieved by using liquid preparations of the alkaline fixing agent in the form of a thickened aqueous solution or in the foamed state thereof as the fixing liquors, and the impregnation process to cover the form or the pre-block with this fixing liquor by means of a uniform application of small amounts of liquid (Minimum order) effecting application measure and that the subsequent heat fixation of the prints or block dyeing on the textile material treated in this way is brought about by long-term steaming in a hanging loop damper.

The principle of the present invention is based on the finding and the practice-oriented implementation of special guidelines for optimal process conditions. By The previously unknown combination of the use of minimal application systems for padding over or splashing over the fixing liquids or foams on the alkali-free form or padding with the reactive dyes together with the subsequent dye fixation in a hanging loop damper according to the present invention succeeds at the beginning to get the problems outlined in the course of the two-phase application of reactive dyes with low fixing speed.

The composition of the alkaline fixing liquor in the claimed process is naturally very different from the recipe in this regard in the case of conventional two-phase short steaming processes. The consistency of the fixing liquors sought in accordance with the invention can be adjusted by adding the aqueous solutions provided for this purpose in addition to alkalis and sodium water glasses, thickeners such as e.g. Alginates, starch or guar derivatives, carboxymethyl celluloses, etc., or electrolytes. Soda water glass is also advantageously considered on its own as the actual agent for fixing the dyes and is not only recommended as an aid for increasing the viscosity of the fixing liquor and for achieving a uniform film on the fixing alkali on the application rollers. In such a case, the liquid preparations contain aqueous solutions based on soda water glasses, which have a degree of flatness of 37-50 ° Be or a specific weight of 1.34 to 1.53.

In the two-phase long steaming method according to the invention, soda water glass is used either alone in a concentration of 200-400 ml per liter of padding liquor or in a mixture with other alkalis, in which case, for example, 100 ml of soda water glass of 38 ° B6 and 10-50 g or ml of soda, potash or caustic soda from 38 ° B6 works.

If the last-mentioned alkali mixture is used as a fixing agent, there is surprisingly the advantage that the sodium hydroxide solution is buffered by the water glass present in the course of the two-phase long-steaming process to such an extent that quantities in the range from 20-100 are not influenced on the stability of the color tones ml of caustic soda of 38 ° Be can add 100 ml of soda water glass of 38 ° Be to the stock. This finding is of particular interest for practical purposes in the case of the production of olive tones that are made up of a large amount of yellow and a small proportion of black (see example 2).

In practice, hanging loop dampers have so far only been used sporadically for two-phase long-steaming processes for the application of vat dyes. For the time being, however, they could not be used for the fixation of prints with reactive dyes because the white bottoms were smeared in the damper using the usual fixing liquors. This negative result is caused by the large goods content of 100-500 m and by a few dozen bars that transport the goods placed in loops in the damper. In contrast, steaming systems for the two-phase short steaming process only have a product content of 4-10 m and 3 deflection rollers.

In the case of the conventional combination of minimal application systems with a pinch joint and the two-phase short steaming method according to the prior art, it has turned out to be a great disadvantage that, as a result of the inadequate equipment, threads and fluff on the surface of the goods and folds at the goods inlet on the first phase Mark pre-printed or pre-padded textile goods so strongly that the dye practically does not fix at these points during the subsequent short-term steaming. Furthermore, the pressure is not always sufficient even with a pressure of 5 bar and the use of a steel roller and you have to Therefore, when making alkaline blocks, make sure that the goods are always on the right side of the rubber roller, which is equipped with a cleaning device.

In the claimed method, on the other hand, it was surprisingly found in this regard that the usual product qualities can be safely padded on the left or right side of the product and that threads and fluff also draw significantly less than in the case of the known two-phase short steaming method.

In the two-phase long-steaming process according to the invention, the minimal application of the fixing liquor takes place with the aid of machine application and metering systems, in which the chemical solution is finely distributed on the uniformly passing fiber material in a coherent layer which is applied or coated over the surfaces previously printed or padded with the dyes. is foamed. The equipment requirements for a minimum order with this orientation are met, for example, by rollers, doctor blades, foam chambers or gear wheels.

In the case of the application of chemical solutions of the type mentioned, the minimal fixing agent application can be carried out by means of measures based on the functional principle or the action of rollers and / or doctor blades. A wide variety of roller application systems with pinch joints are suitable for this, including Rubber or steel rollers, magnetic doctor blades with or without metering device, doctor blades or circular stencils. Paddle rollers to which a scraper is pressed are also suitable.

The foams can be applied according to the method claimed by the invention using various technologies. The foam can either be by doctoring, squeezing, sucking through, indirect doctoring, padding as well as by means of slot nozzles, rotary stencils, foam chambers or according to the principle of a gear pump by speed-controllable gear wheels on the textile material.

According to the present invention, the amount of fixing solution applied is 20-50%, preferably 25-40%, based on the weight of the goods. The steaming time in the hanging loop damper is 2-12 minutes, preferably 3-7 minutes at 105-140 ° C.

Practically all commercially available products with dichloro- and monochlorotriazine-, di- and trichloropyrimidine-, dichloroquinoxaline-, dichloropyridazine-, difluoro-chloropyrimidine-, monofluorotriazine-, fluoro-chloromethyl are suitable as reactive dyes for the new two-phase long-steaming process -pyrimidine, vinyl sulfone, acrylamide and ethyl sulfonamide groups (anchors) as a fiber-reactive system.

The method according to the present invention is intended for the fixation of prints and block dyeing with reactive dyes on sheet-like cellulose fiber materials of natural or regenerated origin and their mixtures with synthetic fibers in all processing stages, such as woven, knitted or nonwoven fabrics.

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 C.I. Reactive Blue 21 are included
• 428 g of hot water dissolved and the solution obtained is in
• 500 g of a 4% aqueous alginate thickener were stirred in. Then you give the print paste preparation
• 10 g of 3-nitrobenzenesulfonic acid sodium and
• Add 2 g of monosodium phosphate.

This printing paste is used to print and dry a knitted fabric made of non-leached cellulose in rouleaux printing. The alkali-free form produced in this way is then subjected to an alkali solution made of 300 ml water glass of 38 ° Be per liter of water (liquor absorption 20%) on a metering knife pad (e.g. foulard with a metering knife of 20/100 mm engraving depth) and immediately thereafter for dye fixation subjected to saturated steam treatment at 105 ° C in a hanging loop steamer for 8 min. Subsequently, the printing stain produced is rinsed cold with water, soaped and dried as usual.

You get a turquoise print on the goods with good fastness properties.

Example 2

• 50 g of C.I. Reactive Yellow 159 and
• 10 g of a black reactive dye based on an Or / Co mixed complex azo compound according to Example 1 of the German patent application DE-A-32 30 102 are treated with
• 428 g of hot water dissolved and the solution obtained is in
• 500 g of a 4% aqueous alginate thickener were stirred in. Then you add the ink base 10 g of 3-nitrobenzenesulfonic acid sodium and
• Add 2 g of monosodium phosphate.

This printing paste is used to print and dry a fabric made from non-leached cellulose in Rouleaux printing. A fixative solution consisting of 100 ml water glass of 38 ° Be, 20 ml sodium hydroxide solution of 38 ° B6 and 880 ml water with a liquor absorption of 30% is then placed on the alkali-free pre-pressure created in the above manner by means of a squeegee roller to which a wiper is pressed. applied and the thus over-clad goods are subsequently exposed to the action of superheated steam in a hanging loop damper at 120 ° C. for 6 minutes. Finally, the patterned goods are post-processed as usual.

A deep olive with good fastness properties is obtained.

When the printing dyeing described above is carried out, the amount of sodium hydroxide solution can be tripled or quintupled without changing the color of the pattern produced. When using padding liquors of the fixing chemicals without the addition of water glass, however, each time the sodium hydroxide solution concentration on the textile is changed, a different shade is obtained.

Example 3

• 50 g of C.I. Reactive Orange 13 are made with the help of
• 438 g of hot water are dissolved and the solution obtained is stirred in
• 500 g of a 4% aqueous alginate thickener entered. Then you give the prepared ink 10 g of 3-nitrobenzenesulfonic acid sodium and
• Add 2 g of monosodium phosphate.

This printing paste is used to print and dry a knitted fabric made from non-leached, modified regenerated cellulose fibers on a rotary film printing machine. Separately, an aqueous, 3% foam is produced which contains 100 ml of 38 ° Be water glass, 30 g soda and 2 g of a surfactant mixture of alkenesulfonates and hydroxyalkanesulfonates in a ratio of 1: 1 per liter of the underlying aqueous liquor (liquid fraction). This foam of the alkaline fixing agent is then by means of a foam distribution and application chamber, as described in German patent DE-C-25 23 062, in an amount corresponding to a liquor absorption of 25% on the previously generated alkali-free form in the form of a uniform thick layer applied. The dye thus applied is then fixed in a hanging loop damper in the course of a steam treatment of 3 minutes at 130 ° C. and the printed textile material is post-treated as usual.

A clear orange with good fastness properties is obtained on the goods.

Example 4

• 40 g of C.I. Reactive Red 151 are with
• Dissolved 448 g of hot water and with careful stirring
• 500 g of a 4% aqueous alginate thickener are mixed.

Then 10 g of 3-nitrobenzenesulfonic acid sodium and 2 g of monosodium phosphate are added to the dye preparation.

With this printing paste, a fabric is now made from mercerisier ter printed and dried in film printing cotton. An alkaline solution of 400 ml water glass of 38 ° Be in 600 ml water with a liquor absorption of 40% is then applied to the resulting alkali-free form by means of a magnetic squeegee without metering device, and the printed textile material is then fixed in one step for dye fixation for 2 min Suspension loop damper treated with superheated steam at 140 ° C.

A deep red is obtained with good fastness properties.

Example 5

• 50 g of C.I. Reactive Blue 166 are in
• 438 g of hot water and dissolved with the solution thus obtained are stirred
• 500 g of a 4% aqueous alginate thickener are charged. Then you give the prepared ink
• 10 g of 3-nitrobenzenesulfonic acid sodium and
• Add 2 g of monosodium phosphate.

This printing paste is then used to print and dry a fabric made from leached cellulose in rotary film printing. Separately, a 6% foam is produced which contains 150 ml water glass of 38 ° Be, 30 ml sodium hydroxide solution of 38 ° Be, 2 g of a surfactant mixture of approximately equal proportions of alkene sulfonates and hydroxyalkane sulfonates and as a foam stabilizer, small amounts of a fatty alcohol per liter of aqueous liquor , contains for example lauryl alcohol. From this foam of the alkaline fixative, a uniform layer, the thickness of which corresponds to a liquor absorption of 20%, is then applied by means of a perforated rotary stencil to the above-mentioned form with the alkali-free printing paste. Then it becomes like this treated goods to bring about the dye fixation for 6 minutes of steam exposure at 110 ° C in a hanging loop damper and aftertreated in the usual way.

A clear blue with good fastness properties is obtained.

Example 6

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

This printing paste is used to print and dry a fabric made of non-leached cellulose in rouleaux printing. Thereafter, the goods pre-printed in this way are padded with an alkaline fixing solution as described in Example 1, steamed for dye fixation and finally finished.

A deep black with good fastness properties is obtained.

Example 7

• 30 g of C.I. 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 C.I. Reactive Blue 19 (C.I.No. 61 200) with the help of
• 270 g of boiling water dissolved. Both approaches are then in
• 400 g of cold water entered, which contains 4 g / 1 of a wetting agent and 20 g / 1 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.

The cooled goods are then padded, steamed and, as usual, aftertreated and dried in accordance with the instructions of Example 5 to fix the reactive dye with the alkaline liquor specified therein.

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

Example 8

• 50 g of C.I. Reactive Red 35 are being moved with
• Dissolved 438 g of hot water and the resulting solution is in
• 500 g of a 4% aqueous alginate thickener were stirred in. Then you add the ink preparation prepared in this way
• 10 g of 3-nitrobenzenesulfonic acid sodium and
• Add 2 g of monosodium phosphate.

This printing paste is now used to print a fabric made of mercerized cotton on a Rouleaux printing machine and dried. Separately, an aqueous, 10% foam of the alkaline fixative (1 1 foam weighs 100 g) is produced, which calculates 30 g of soda per kg of the underlying aqueous liquor fraction (before foaming), 100 g of table salt, 200 g of a 5% , aqueous solution of a thickener based on a guar derivative (or another type customary in textile printing) and 5 g of a surfactant mixture of alkenesulfonates and hydroxyalkanesulfonates in a ratio of 1: 1. The foamed fixative is then applied to the previously produced print with the alkali-free dye preparation using a perforated rotary stencil, the weight of which corresponds to a liquor absorption of 30%. Thereupon, the goods treated in this way are subjected to the effect of steam at 110 ° C. in a hanging loop damper for 6 minutes in order to bring about the dye fixation and are subsequently treated in a conventional manner.

A deep red is obtained with good fastness properties.

Example 9

• 50 g of C.I. Reactive Yellow 37 are treated with
• 438 g of hot water are dissolved and with this solution are mixed well
• 500 g of a 4% aqueous alginate thickener are charged. Then you add the prepared ink preparation
• 10 g of 3-nitrobenzenesulfonic acid sodium and
• Add 2 g of monosodium phosphate.

With the printing paste thus created, a fabric made of mercerized cotton is now printed on a Rouleaux printing machine and dried. Separately, one becomes aqueous, 10% foam of the alkaline fixing agent (1 1 foam weighs 100 g), which calculates 30 g of soda, 150 g of sodium chloride and 5 g of a surfactant mixture from about the same per kg of the starting aqueous formulation (before foaming) Has proportions of alkenesulfonates and hydroxyalkanesulfonates. This foamed fixative is then applied to the above-mentioned alkali-free print by means of a perforated rotary stencil, applying a uniform layer, the weight of which corresponds to a liquor absorption of 30%. The treated product is then applied for a period of 6 minutes to effect dye fixation exposed to steam at 110 ° C in a hanging loop damper and then finished as usual.

A brilliant yellow is obtained with good fastness properties.

Claims (6)

1. Process for the continuous fixing of prints and block dyeing with reactive dyes on textile webs made of cellulose fibers or their mixtures with synthetic fibers, preferably with polyester fibers, according to a two-phase steaming technique, the dissolved alkaline fixing agent being in the form of minimal amounts of liquor on the unfixed, is applied beforehand with the reactive dyes without alkali added or block-dyed and optionally dried fiber material, characterized in that liquid preparations of the alkaline fixative in the form of a thickened aqueous solution or in the foamed state thereof are used as the fixing liquors, and the impregnation process to cover the pre-pressure or the pre-block with this fixing liquor by means of an application measure which effects the uniform application of small amounts of liquid (minimal application), and that the subsequent heat fixing of the prints or blocks Colorings on the textile material treated in this way are brought about by long-term steaming in a hanging loop damper. 2. The method according to claim 1, characterized in that liquid preparations are used as fixing liquors which, in addition to aqueous solutions of alkalis, also contain sodium water glasses, thickeners or electrolytes. 3. The method according to claim 1, characterized in that liquid preparations are used as fixing liquors, which aqueous solutions based on soda water glasses having a degree of 37-50 ° B6 or a specific weight of 1.34 to 1.53, optionally in a mixture with other alkalis. 4. The method according to claims 1 to 3, characterized in that the minimum order of the fixing liquor is accomplished with the aid of rollers, doctor blades, foam chambers or gears as a machine application and metering system. 5. The method according to claims 1 or 4, characterized in that the minimum order causes a liquor absorption of the textile goods of 20 to 50% (based on the weight of the dry goods) on the fixing liquor. 6. The method according to claims 1 to 5, characterized in that the fixation of the prints or block dyeing in a hanging loop damper at 105 ° to 140 ° C in a period of 2 to 12 minutes.