EP0019861B1 - Process for the even dyeing of mixtures of cellulosic fibres and synthetic polyamide fibres - Google Patents

Abstract

1. A process for the uniform dyeing of textile material made from mixtures of cellulosic fibers and synthetic polyamide fibers and, if desired, additionally elastomeric fibers on polyurethane basis, according to the exhaust dyeing technique, which comprises treating the foregoing defined fiber mixtures for 30 to 60 minutes at temperatures of from 60 to 110 degrees C with an aqueous liquor containing alkaline reducing agents in addition to sulfur dyestuffs and certain metal-complex dyestuffs and/or acid dyestuffs being selected due to the result of an experimental dyeing test as specified below, whereupon the reoxidation of the applied sulfur dyestuffs present in the leuco-form is performed in usual manner, and in which process the metal-complex dyestuffs and acid dyestuffs to be used have to meet the following requirements : Dyeings A (comparison dyeing) and Dyeing B (test dyeing) which have been prepared using the dyestuff to be examined according to the recipes Dyeing A with 2% of said dyestuff, 3% of sodium acetate and 3% of acetic acid (60% strength) ; Dyeing B with 2% of said dyestuff, 10 cc/l of NaHS-solution (21% strength), 5 g/l of sodium carbonate (calc.) and 10 g/l of sodium sulfate (calc.) ; each time on two samples of a hank having the same weight and containing 100% of synthetic polyamide fibers on the one hand and 100% of cotton on the other hand, in an aqueous liquor at a goods-to-liquor ratio of 1:10, in which dyeing operation in both cases the samples having been introduced into the liquor at 30 degrees C and treated therein for 10 minutes at 30 degrees C, then heated to 95 degrees C within 20 minutes and dyed during 60 minutes at 95 degrees C, subsequently rinsed and dried, must not differ from one another in the shade on the synthetic polyamide fiber while the cotton being stained by the dyestuff as poor as possible, and Dyeing B must in shade not be lighter more than 10% in comparison with Dyeing A.

Description

The present invention relates to a process for the uniform dyeing of textile material from mixtures of cellulose fibers with synthetic polyamide fibers and, if appropriate, elastomer fibers based on polyurethane using the pull-out dyeing technique.

A number of process variants are known and have been put into practice for the dyeing of fiber mixtures of the type mentioned above. In the case of low authenticity requirements for the colored articles, such dyeings can be carried out in a single bath with acid dyes and direct dyes in a weakly acidified or neutral liquor. However, if there are higher authenticity requirements, the goods must be treated with the dyes suitable for the fiber components in two baths or at least two stages. One of the two types of fibers is pre-dyed in the first bath (1st stage) and the other is covered in the second dyebath (2nd stage). With two-step procedures of this type, it is only in the rarest of cases possible to use dyes from different dye classes side by side in the same bath from the start of dyeing. Most of the time, in the conventional exhaust process, one is strictly bound to a certain sequence of the dye additive in question, so that useful colorations result.

Methods with the above-mentioned objective are described, for example, in ICI Technical Information D 1406 "Dyeing textiles from polyamide / cellulose mixtures", in Technology of Textile Industry U.S.S.R. 1971, No. 1, page 88 ff. And in Textilpraxis 71, issue 10, pages 632-635 and issue 11, pages 686-689.

However, no processes have so far become known in which dyes which have to be reduced for their application can be used at the same time with other classes of dyes for dyeing cellulose fiber / polyamide fiber mixtures.

In recent times, textiles made from such blends of cellulose fibers with synthetic polyamide fibers have become increasingly important for casual wear, to which higher authenticity requirements are placed. The stretch cord article made of 80% cotton, 16% polyamide fiber and 4% elastomer fiber based on polyurethane should be mentioned here.

The sought-after authenticity properties as well as the diverse color shades within the available color palette together with extremely economical applicability make sulfur dyes very interesting for dyeing the fiber mixtures mentioned. Their use on a practical scale, however, stands in the way that they have to be dyed with the aid of reducing agents, which, according to the previous view, makes cumbersome, then no longer economical, two-bath dyeing methods necessary, which are too complex for the intended purpose.

The invention is based on the object of developing a simple and, if possible, single-bath process for dyeing mixtures of cellulose fibers and synthetic polyamide fibers with the use of sulfur dyes, with both fiber portions being dyed with a matching shade.

It has now been found that textile material made from mixtures of cellulose fibers with synthetic polyamide fibers and, where appropriate, polyurethane-based elastomer fibers can be dyed uniformly using the exhaust dyeing technique by using the fiber mixtures mentioned in an aqueous alkaline dye bath containing reducing agents for 30 to 60 minutes at temperatures of 60 ° to 110 ° C simultaneously treated with sulfur dyes and selected (as defined below) metal complex dyes and / or acid dyes, whereupon the reoxidation of the sulfur dyes applied as a leuco compound is brought about in the usual way. The tone-on-tone dyeings achieved on the basis of the measures according to the invention meet the increased authenticity requirements which are placed on casual clothing.

According to the process, suitable chemicals are the reducing agents which are customarily used in the dyeing of sulfur dyes, such as sodium sulfide or sodium hydrogen sulfide / soda, in each case alone or in a mixture.

A supplementary addition of a sodium polysulfide of the formula Na ₂ S _2-. to the reducing agents mentioned above proves to be favorable for stabilizing the reduction conditions.

Furthermore, glucose / sodium hydroxide solution and, if the sulfur dyes are suitable for dyeing with hydrosulfite, hydrosulfite (sodium dithionite) / alkali can also be used as the reducing agent.

The feasibility of such a process has hitherto been considered impossible, on the one hand because of the known relative sensitivity to reduction of the metal complex and acid dyes which are generally azo compounds and on the other hand because of the known susceptibility to demetallization, i.e. Destruction of the metal complex dyes in alkaline or sulfide-containing dyeing liquors or other wet treatment baths.

It is therefore surprising that various representatives of the dye categories just discussed survive the harsh conditions of sulfur dye fixation (alkali, reducing agents, temperatures above 60 ° C) without impairing the color tone and dye yield, and that the synthetic polyamide fibers also survive in the alkaline dye bath can be stained with the usual fastness properties and practically without loss of color depth.

The method according to the invention thus enables the fiber mixtures mentioned to be dyed with the required high level of fastness while maintaining all the dyeing advantages, such as single-bath, economical dyeing with little expenditure of time and less waste water.

According to the new process, all types of sulfur dyes, including leucosulfur dyes and the water-solubilized sulfur dyes listed in the COLOR INDEX as "Solubilized Sulfur Dyes" are suitable as sulfur dyes.

• Man behandelt mit dem in Aussicht genommenen Farbstoff - zweimal unter verschiedenen Bedingungen - jeweils zwei Strängchen von gleichem Gewicht (trockene Ware) aus
  • a) 100% synthetischen polyamidfasern sowie
  • b) 100% Baumwolle
  
  zusammen im gleichen wäßrigen Bad bei einem Flottenverhältnis von 1:10 (bezogen auf das Gesamtgewicht) nach den unten aufgeführten Rezepten (Prozentangaben bedeuten Gewichtsprozent):
  • A) Vergleichsfärbung
    • 2% Farbstoff,
    • 3% Natriumacetat und
    • 3% Essigsäure (60 %ig).
  • B) Testfärbung
    • 2% Farbstoff,
    • 10 cm³/I einer 21 %igen Natriumhydrogensulfid-Lösung,
    • 5 g/I Soda kalz. und
    • 20 g/I Glaubersalz kalz.

The metal complex dyes and acid dyes are subjected to the following test criteria to determine their suitability for the inventive method:

• One treats with the envisaged dye - twice under different conditions - two strands of the same weight (dry goods)
  • a) 100% synthetic polyamide fibers as well
  • b) 100% cotton
  
  together in the same aqueous bath at a liquor ratio of 1:10 (based on the total weight) according to the recipes listed below (percentages mean percentages by weight):
  • A) Comparative staining
    • 2% dye,
    • 3% sodium acetate and
    • 3% acetic acid (60%).
  • B) test staining
    • 2% dye,
    • 10 cm ³ / l of a 21% sodium hydrogen sulfide solution,
    • 5 g / l soda ash. and
    • 20 g / I Glauber's salt calc.

In both cases, the samples are entered into the shared bath at 30 ° C. and are allowed to run for 10 minutes at the set start temperature; the liquor and dyeing samples are then heated to 95.degree. C. in the course of 20 minutes and the dyeing is finally completed at 95.degree. C. in the course of a further 60 minutes. After rinsing and drying, the test color B obtained in this way is compared with the color A ..

Suitable for the purposes of the present invention are those metal complex or acid dyes whose test dye B on the synthetic polyamide fiber does not deviate in color with the dye A to be compared and whose color depth does not appear to be more than 10% lighter than dye A. At the same time, however, the cotton skein should only be slightly stained. If a dye tested in this way proves to be resistant to the effects of the above chemicals under the test conditions used, then it will be so even with a longer treatment time if it is used in practice.

Selected metal complex dyes can also be used in a mixture with the selected acid dyes for the dyeing operation.

The process according to the invention can be used to dye mixtures of cellulose fibers and synthetic polyamide fibers in virtually all mixing ratios and processing conditions, e.g. in the form of a thread or in the form of finished woven or knitted piece goods, in the appropriate dyeing machines.

To carry out the new process, the aqueous dyebath, which can have a liquor ratio of 1: 2 to 1:50, is initially at about 30 ° C. with the necessary reducing agents and alkaline substances for the reduction of the sulfur dyes, and possibly still other necessary aids (such as wetting agents, leveling aids, etc.). Now the fiber material to be dyed is introduced into this dye-free liquor and pretreated for 5 to 10 minutes under the given temperature conditions. Then the dyes already present as liquid brands or the dissolved dyes are added to the bath. Usually, the sulfur dyes and the metal complex or acid dyes are dissolved individually and the separately prepared solutions are only brought together in the dyebath. The liquor temperature is then raised to the fixing conditions for the dyes from 60 ° C. to 110 ° C. within 20 minutes, the range from 90 ° C. to 100 ° C. being preferred, and the textile material is dyed for 30 to 60 minutes this temperature. About 5 to 10 minutes after the dyeing temperature has been reached, 10 to 30 g / l of sodium chloride are added to the bath.

After the required dyeing time has passed, the dyeing liquor is drained off and the textile goods treated in this way are rinsed; then the sulfur dye applied in leuco form is developed according to one of the known methods for oxidation, the dyeing is rinsed again and finally completed.

If the dyes referred to in the COLOR INDEX as "Solubilized Sulfur Dyes" are used as sulfur dyes to carry out the dyeing operation, then in accordance with the invention a two-stage, but single-bath process, which is therefore still simplified compared to the prior art, can be carried out, in which in the course of the first stage in the presence of acid. Then you neutralize this acidic fleet, which is now the necessary reduction medium and alkaline substances are added, whereupon the coloring is now completed in a reduced, alkaline bath.

example 1

• 4 g/I Soda kalz.
• 8 cm³/1 einer 21 %igen Natriumhydrogensulfid-Lösung sowie
• 3 cm³/1 einer Lösung mit einem Gehalt an 20% Na-polysulfid, 14% Na₂S und 3% Na₂S₂O₃,

und behandelt damit das Textilgut 10 Minuten lang bei der gegebenen Temperatur. Diesem Färbebad setzt man nun (die %-Angaben sind bezogen auf das Gewicht der trockenen Ware)

• 2,4% des Farbstoffs der C.I.-Nr. 53 271 (Solubilised Sulphur Brown 15),
• 3% des Farbstoffs der C.L-Nr. 53 056 (Solubilised Sulphur Brown 10) und
• 1 % des Farbstoffs der C.I.-Nr. 53 186 (Solubilised Sulphur Black 1),

jeweils gelöst in heißem Wasser, hinzu und sodann, ebenfalls in heißem Wasser gelöst, noch

• 0,45% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  
• 0,16% des 1:2-Chromkompiexes des Azofarbstoffes der Formel
  
• und 0,16% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  

die Metallkomplexfarbstoffe jeweils in handelsüblicher Form.In a reel runner, 80 kg of a stretch cord made of 80% cotton and 4% polyurethane elastomer threads, which are wound with 16% polyamide threads, are to be dyed in a liquor ratio of 1:20. For this purpose, an aqueous dye bath at 30 ° C. is charged with

• 4 g / l soda calc.
• 8 cm ^{3/1 of} a 21% sodium hydrogen sulfide solution as well
• 3 ^cm3 / 1 of a solution with a content of 20% Na-polysulfide, 14% Na ₂ S and 3% Na ₂ S ₂ O _3,

and uses it to treat the textile at the given temperature for 10 minutes. This dye bath is now set (the percentages are based on the weight of the dry goods)

• 2.4% of the dye of the CI no. 53 271 (Solubilized Sulfur Brown 15),
• 3% of the dye of CL no. 53 056 (Solubilized Sulfur Brown 10) and
• 1% of the dye of CI no. 53 186 (Solubilized Sulfur Black 1),

each dissolved in hot water, and then, also dissolved in hot water, still

• 0.45% of the 1: 2 chromium complex of the azo dye of the formula
  
• 0.16% of the 1: 2 chromium complex of the azo dye of the formula
  
• and 0.16% of the 1: 2 chromium complex of the azo dye of the formula
  

the metal complex dyes each in a commercially available form.

After a treatment time of 10 minutes, the dyebath is heated to 95 ° C. in the course of 30 minutes and the goods are first dyed at this temperature for 10 minutes. After adding 20 g / l of sodium chloride, the hot liquor is then allowed to act on the textile material at 95 ° C. for a further 30 minutes. The dye liquor is then drained off and the dyeing is rinsed clear.

• 1,2% Natriumbichromat und
• 3% Essigsäure (60 %ig)

während 20 Minuten bei 70°C oxidiert und die so hergestellte Färbung abschließend mit Wasser wieder klar gespült und getrocknet.The sulfur dye applied as a result of the previous measures in leuco form is now contained by treatment with a fresh aqueous bath

• 1.2% sodium bichromate and
• 3% acetic acid (60%)

oxidized at 70 ° C. for 20 minutes and the dyeing thus produced was finally rinsed clear with water and dried.

The result is a powerful, fashionable brown shade with very good tone-on-tone color of the tree wanted ^p ol and Polyamidumspinnung the elastomeric fiber. The stretch properties of the cord are not affected.

Example 2

• 4 g/I Soda kalz.,
• 3,5 cm³/1 einer 21 %igen Natriumhydrogensulfid-Lösung sowie
• 5 cm³ I einer Polysulfid-Lösung gemäß Beispiel 1.

72 kg of a mixed fabric made of 80% cotton and 20% polyamide are to be dyed in a jet dyeing machine, the liquor ratio being 1:15. To do this, load the jet dyeing machine with the dye and water at 30 ° C and add this liquor

• 4 g / l soda soda,
• 3.5 cm ^{3/1 of} a 21% sodium hydrogen sulfide solution as well
• 5 cm ³ I of a polysulfide solution according to Example 1.

• 5% des Farbstoffes der C.l.-Nr. 53 005 (Leuco Sulphur Green 9) und
• 1,6% des Farbstoffes der C.l.-Nr. 53 327 (Leuco Sulphur Brown 51)

ferner separat von den Schwefelfarbstoffen gelöst, noch

• 0,1% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  
• 0,3% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  
• und 0,04% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  

After about 5 minutes, the following dyes (in a commercially available form), each dissolved in hot water, are added to the bath in the amounts specified below (the percentages are based on the weight of the dry paint):

• 5% of the dye of Cl no. 53 005 (Leuco Sulfur Green 9) and
• 1.6% of the dye of Cl no. 53 327 (Leuco Sulfur Brown 51)

further separately from the sulfur dyes, still

• 0.1% of the 1: 2 chromium complex of the azo dye of the formula
  
• 0.3% of the 1: 2 chromium complex of the azo dye of the formula
  
• and 0.04% of the 1: 2 chromium complex of the azo dye of the formula
  

After an exposure time of 5 minutes at 30 ° C, the liquor is heated within 20 minutes to 95 ° C and dyes the goods for 5 minutes at this temperature. Then 20 g / l of sodium chloride are added to the bath and the coloration is completed at 95 ° C. over a further 30 minutes. The liquor is then drained off and the fabric is rinsed clear with water.

• 1,2% Wasserstoffperoxid (33 %ig) und
• 1 g/I Soda kalz.

auf der Faser oxidiert und danach wird das gefärbte Material mittels Wasser wieder klar gespült und getrocknet.The leuco dye is then treated by treatment for 10 minutes at 40 ° C. in a fresh aqueous bath with the addition of

• 1.2% hydrogen peroxide (33%) and
• 1 g / l soda ash.

oxidized on the fiber and then the dyed material is rinsed clear with water and dried.

A strong, uniform olive shade is obtained on the cotton and polyamide fibers with very good tone-on-tone coloring of the different types of fibers.

Example 3

• 1 g/I eines SequestriermitteJs auf Basis von Aethylendiamin-tetraessigsaurem Natrium,
• 4 g/I Soda kalz.,
• 10 cm³/1 einer 21 %igen Natriumhydrogensulfidlösung sowie
• 3 cm³/1 einer Lösung mit einem Gehalt an 22% Natriumpolysulfid, 10% Na₂S und 3% Na₂S₂0₃,

und läßt die Ware 1 Passage blind, d.h. ohne Farbstoffzusatz vorlaufen. Die zur Färbung vorgesehenen Farbstoffe, welche vor ihrem Zusatz zur Flotte in heißem Wasser gelöst werden (die %-Angaben beziehen sich auf das Gewicht der trockenen Ware), sind folgende:

• a) 5% des Farbstoffes der C.I.-Nr 53 328 (Solubilised Sulphur Brown 51),
  • 2% des Farbstoffes der C.l-Nr. 53 271 (Solubilised Sulphur Brown 15) und
  • 0,55% des Farbstoffes der C.l-Nr. 53 186 (Solubilised Sulphur Black 1), sowie
• b) 0,4% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  
  0,2% des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  
  und 0,21 des 1:2-Chromkomplexes des Azofarbstoffes der Formel
  

120 kg of stretch cord made of polyamide / cotton should be dyed in a jigger with a liquor ratio of 1: 5 as in Example 1. For this task, the jigger is loaded with the fiber material, the dye bath is mixed with water at 30 ° C and loaded with it

• 1 g / l of a sequestering agent based on ethylenediaminetetraacetic acid sodium,
• 4 g / l soda soda,
• 10 cm ^{3/1 of} a 21% sodium hydrogen sulfide solution and
• 3 cm ^{3/1 of} a solution containing 22% sodium polysulfide, 10% Na ₂ S and 3% Na ₂ S ₂ 0 ₃ ,

and lets the goods run 1 passage blind, ie without the addition of colorants. The dyes intended for dyeing, which are dissolved in hot water before being added to the liquor (the% data relate to the weight of the dry goods) are as follows:

• a) 5% of the dye of CI No. 53 328 (Solubilized Sulfur Brown 51),
  • 2% of the dye of the Cl no. 53 271 (Solubilized Sulfur Brown 15) and
  • 0.55% of the dye of Cl no. 53 186 (Solubilized Sulfur Black 1), and
• b) 0.4% of the 1: 2 chromium complex of the azo dye of the formula
  
  0.2% of the 1: 2 chromium complex of the azo dye of the formula
  
  and 0.21 of the 1: 2 chromium complex of the azo dye of the formula
  

These previously listed dye mixtures a) and b) are evenly passed through on both ends.

• 1,2% Bichromat und
• 3% Essigsäure (60 %ig)

auf der Faser oxidiert. Abermaliges Klarspülen der gefärbten Ware mit Wasser beendet schließlich den Färbeprozeß.Textile goods distributed to the fleet. After a further 2 passages for FI _Q compensation, the bath is heated to 95 ° C and the goods are treated 1 pass at this temperature. Now 20 gl Glauber's salt is distributed over 2 ends. fed and the dyeing is continued at 95 ° C over a further 30 minutes. Then the textile material is rinsed clear with water, whereupon the sulfur dye present in leuco form is obtained by treatment at 70 ° C. with an aqueous bath

• 1.2% bichromate and
• 3% acetic acid (60%)

oxidized on the fiber. Repeated rinsing of the dyed goods with water finally ends the dyeing process.

After drying, a level dark brown coloration of the cord is obtained which matches the color shade well on polyamide fibers and cotton.

Claims (1)

1. A process for the uniform dyeing of textile material made from mixtures of cellulosic fibers and synthetic polyamide fibers and, if desired, additionally elastomeric fibers on polyurethane basis, according to the exhaust dyeing technique, which comprises treating the foregoing defined fiber mixtures for 30 to 60 minutes at temperatures of from 60 to 110°C with an aqueous liquor containing alkaline reducing agents in addition to sulfur dyestuffs and certain metal-complex dyestuffs and/or acid dyestuffs being selected due to the result of an experimental dyeing test as specified below, whereupon the reoxidation of the applied sulfur dyestuffs present in the leuco-form is performed in usual manner, and in which process the metal-complex dyestuffs and acid dyestuffs to be used have to meet the following requirements:

   Dyeings A (comparison dyeing) and Dyeing B (test dyeing) which have been prepared using the dyestuff to be examined according to the recipes

   Dyeing A with 2% of said dyestuff,

   3% of sodium acetate and

   3% of acetic acid (60% strength);

   Dyeing B with 2% of said dyestuff,

   10 cc/I of NaHS-solution (21% strength),

   5 g/I of sodium carbonate (calc.) and

   10 g/I of sodium sulfate (calc.);

   
   each time on two samples of a hank having the same weight and containing 100% of synthetic polyamide fibers on the one hand and 100% of cotton on the other hand, in an aqueous liquor at a goods-to-liquor ratio of 1:10, in which dyeing operation in both cases the samples having been introduced into the liquor at 30°C and treated therein for 10 minutes at 30°C, then heated to 95°C within 20 minutes and dyed during 60 minutes at 95°C, subsequently rinsed and dried, must not differ from one another in the shade on the synthetic polyamide fiber while the cotton being stained by the dyestuff as poor as possible, and Dyeing B must in shade not be lighter more than 10% in comparison with Dyeing A.