EP0014852A1 - Process for the continuous or semi-continuous dyeing of mixtures of cellulose fibres and synthetic polyamide fibres with azo developing dyestuffs - Google Patents

Abstract

1. A process for the uniform tone-in-tone dyeing of textile woven or knit fabrics made from mixtures of cellulose fibres and synthetic polyamide fibres according to a continuous or semi-continuous method of the pad-dyeing technique from a single bath with water-insoluble azo dyestuffs formed on the fibre from coupling component and diazo component in the form of a stabilized diazonium compound, in which the dyestuff components are mutually applied under alkaline conditions and dyestuff development is caused by the action of acid, which process comprises using as the diazo component a wate-soluble diazoamino compound obtained from a diazotized, aromatic or heterocyclic amine and cyanamide, padding the textile goods at temperatures ranging of from 60 degrees to 70 degrees C with an aqueous, alcoholic liquor containing both of dyestuff components in dissolved form, and wherein - immediately after the padding operation but before effecting the acid treatment, which is necessary for liberating the diazonium compound and coupling - the said impregnated textile goods are steamed without intermediate drying.

Description

The present invention relates to a process for the continuous or semi-continuous, single-bath, uniform tone-in-tone dyeing of textile fabrics or knitted fabrics from mixtures of cellulose fibers and synthetic polyamide fibers by a block dyeing technique with a coupling component and a diazo component in the form of a stabilized diazonium compound Insoluble azo dyes produced on the fiber by applying the dye components together under alkaline conditions and the dye development being brought about by the action of acid.

Continuous methods for dyeing textile articles with so-called development dyes according to the ice dye technique are well known. They are all based on the principle of assembling the insoluble dye on the fiber from two relatively small, soluble and well-diffusing sections.

A single bath procedure is increasing among these working methods Production of water-insoluble azo dyes on cellulose fibers has a special position in which, in addition to a coupling component (hereinafter referred to as "naphthol"), a diazonium compound which is stabilized by reaction of the diazotized amine with cyanamide and is therefore not readily capable of coupling (hereinafter referred to as " Diazo salt ") is padded onto the goods and the coupling-capable diazonium compound is subsequently released again by an acid treatment and is brought into coupling with the" naphthol ". This process, which does not require diazotization on the fiber and, for this reason, is easier to use than the classic dyeing method on cotton, is described in DE-PS 1 262 957 and is also described in the information document from Hoechst Aktiengesellschaft "Technical Council from Hoechst" / Textile No. 224 explained for implementation in practice.

The dyeing of synthetic polyamide fibers with development dyes is also known, but has never been of great importance because of the process steps to be used, which include a change of liquor. Here, the polyamide fiber material with a liquor of an alkaline solute "Naphthol" and a stabilized by _T riazinbildung not couplable water-insoluble diazonium compound dyed in the form of a fine dispersion for a pull-out procedure, and then the dye coupling after cleavage of the stabilizing moiety of the two Components brought about by treatment in a hot development bath containing sulfuric acid.

Mixtures of such polyamide fibers and cellulose fibers can only be dyed using the ice dye technique in a laborious way by using the pull-out process described above with the joint use of "naphthol" and the stabilized, water-insoluble diazonium Combined with the traditional way of dyeing cotton. In this case, before the treatment with sulfuric acid - for dye formation (from "naphthol" and the "diazo salt") on the polyamide fiber component - the color on the cellulose fiber portion of the mixture is developed by developing (from the "naphthol") with an additional, couplable Diazonium compound - with the same aromatic amine as the base - generated. See Melliand Textile Reports 40/1959, No. 3, pages 295-300 and the information leaflet of Hoechst Aktiengesellschaft Hoe 2314 "(R) Ofna-perl Salz BBA".

A continuous or semi-continuous procedure for dyeing both types of fibers at the same time is not known.

In recent times, a textile article made of polyurethane threads spun with synthetic polyamide threads and cotton - in practice referred to as stretch cords - has become increasingly important. Because of the tightness of the polyamide encapsulation, the polyurethane fiber itself does not need to be dyed, provided the polyamide threads can be dyed tone-on-tone with the cotton pile.

It was therefore an object of the present invention to dye mixtures containing polyamide fibers and cellulose fibers uniformly and from a dye bath using a coupling or diazonium component from ice-dye technology in a continuous or semi-continuous process.

This object is achieved according to the invention in that a water-soluble diazoamino compound composed of a diazotized, aromatic or heterocyclic amine and cyanamide is used as the diazo component in that both dye components are dissolved in an aqueous, alcohol-containing liquor at from 60 ° to 70 ° C. Pads textile and that this primer is damped immediately after padding and before the acid treatment necessary to release the diazonium compound and coupling without intermediate drying.

• Es war für den Fachmann überraschend, daß durch die einfache Maßnahme, die beiden Farbstoffkomponenten bei 60° bis 70°C zu klotzen und das so geklotzte Färbegut noch in feuchtem Zustand zu dämpfen, sich eine derart gute Verteilung dieser Komponenten in den Polyamid- und Cellulosefaseranteilen erreichen läßt, daß nach der Säurebehandlung eine Ton-in-Ton-Färbung beider Faserarten resultiert.

However, the dyeing result obtained in the course of the process according to the invention could not be expected without further ado:

• It was surprising for the person skilled in the art that the simple measure of padding the two dye components at 60 ° to 70 ° C. and steaming the dyed material so clogged while still moist resulted in such a good distribution of these components in the polyamide and cellulose fiber fractions can achieve that after the acid treatment results in a tone-in-tone dyeing of both types of fibers.

In the known continuous or semi-continuous processes of ice color technology, the fiber material has previously been padded close to the cooking temperature in order to reduce the substantivity of the "naphthols" and to obtain the same colors. If you use this temperature to dye polyamide-cellulose fiber mixtures, you get false stains because it is not possible to apply the dye components evenly to both types of fiber.

Efforts to apply only the "naphthol" evenly to the material to be dyed from such fiber mixtures, with the aim of then producing uniform colors when coupling with a diazonium compound capable of coupling, have also failed. They only led to the coloring of the cellulose fiber portion of the goods.

Stock response to "Naphthol" and "diazo salt" together at 60 ° to 70 ° C to the fiber mixture and attempts arbstoffkomponenten the uniform distribution of these applied _F be achieved by an intermediate drying, is likewise obtained a greatly the cellulose fiber Favor _coloration.

• a) Verwendung der mit Cyanamid stabilisierten DiazoniumVerbindungen,
• b) Klotzen bei 60° bis 70°C und
• c) Dämpfen vor der Farbstoffentwichlung

führt, zu der geforderten, gleichmäßigen Färbung von Polyamid- und Cellulosefaseranteilen der Mischung.Just the interaction of the three factors

• a) use of the diazonium compounds stabilized with cyanamide,
• b) padding at 60 ° to 70 ° C and
• c) Steaming before dye development

leads to the required uniform coloring of polyamide and cellulose fiber parts of the mixture.

For the first time, it was possible to dye polyamide-cellulose fiber blends in one bath with azo dyes produced on the fibers using a block method of ice dye technology. This one-bath method also offers advantages in terms of energy consumption and water consumption and, in connection therewith, also the amount of waste water compared to previous methods of dyeing such articles.

To carry out the process according to the invention, the coupling component and the “diazo salt” are dissolved in accordance with the dissolving instructions of the manufacturers and added to the padding liquor which is 60 ° to 70 ° C. and which contains the customary chemicals.

The use of an otherwise usual protective colloid based on sulfite waste liquor is avoided in order to avoid damage to the "diazo salt" under the conditions of the new process. To the Endengleichkeit of the dyeings at the padding, at the otherwise unusual Klotz temperature (60 ° to 70 ° C) to ensure the padding liquor advantageously 20 to 100 cm ^3/1 ethanol was added.

The fiber mixtures themselves are padded at 60 ° to 70 ° C on one of the usual padding pad machines with 60 to 100% liquor absorption (based on the weight of the dry goods).

Immediately after padding, i.e. the primed textile is steamed without prior drying. Steaming is carried out at temperatures of 101 ° to 107 ° C., preferably 103 ° to 105 ° C., and at steaming times of 30 seconds to 5 minutes, preferably shorter, namely 30 seconds to 2 minutes. If an HT damper is present, the goods can also be steamed at 120 ° to 135 ° C. for 30 to 120 seconds without the result of the tone-in-tone coloring being impaired.

• kontinuierlich durch Klotzen mit der Säure oder durch eine Säurepassage in einer Breitwaschmaschine, oder halbkontinuierlich im Jigger.

After steaming, the acid treatment of the fiber material treated with the dye components is carried out in a fresh bath to bring about the coupling ability of the "diazo salt" and dye coupling by one of the three usual methods:

• continuously by padding with the acid or through an acid passage in a wide washing machine, or semi-continuously in the jigger.

When using "naphthols", which the dye manufacturers have described as low-substantive, drying the dyed material after steaming can further increase the color yield.

The dye components for the new process are the Color Index, 3rd edition 1971, as Azoic Coupling Components ("Naphthole") and the diazoamino compounds obtained by reaction with cyanamide of the diazotized chemical compounds listed as Azoic Diazo Components ("Diazo salts") in question.

Of the "naphthols" are preferred for the block process as the low to medium substantive products used.

• Azoic Coupling Component 2 mit der C.I.-Nr. 37 505
• Azoic Coupling Component 18 mit der C.I.-Nr. 37 520
• Azoic Coupling Component 20 mit der C.I.-Nr. 37 530
• Azoic Coupling Component 4 mit der C.I.-Nr. 37 560
• Azoic Coupling Component 12 mit der C.I.-Nr. 37 550.

Above all, they are

• Azoic Coupling Component 2 with the CI no. 37 505
• Azoic Coupling Component 18 with the CI no. 37 520
• Azoic Coupling Component 20 with the CI no. 37 530
• Azoic Coupling Component 4 with the CI no. 37 560
• Azoic Coupling Component 12 with the CI no. 37 550.

• Azoic Diazo Component 2 mit der C.I.-Nr. 37 005
• Azoic Diazo Component 46 mit der C.I.-Nr. 37 080
• Azoic Diazo Component 5 mit der C.I.-Nr. 37 125
• Azoic Diazo Component 32 mit der C.I.-Nr. 37 090
• Azoic Diazo Component 11 mit der C.I.-Nr. 37 085.

Of the "diazo salts" which are preferably suitable according to the invention, the derivatives of:

• Azoic Diazo Component 2 with the CI no. 37 005
• Azoic Diazo Component 46 with CI no. 37 080
• Azoic Diazo Component 5 with the CI no. 37 125
• Azoic Diazo Component 32 with the CI no. 37 090
• Azoic Diazo Component 11 with the CI no. 37 085.

The new process can be used for any type of blended fabrics and blended fabrics made of cellulose and polyamide fibers in any mixing ratio. The main thing is to dye stretch cord fabrics and knitted fabrics for outerwear, such as nickies and tracksuits.

The percent (%) designation used in the following exemplary embodiments of information about the composition of the fiber mixture or for the strength of the chemicals relates to “percent by weight”.

example 1

• Lösung 1: Man löst in 70 1 Wasser von 70°C 400 g Oleylmethyltaurin und danach 8,8 kg der Cyanamid-Verbindung aus dem Diazoniumsalz von Azoic Diazo Component46 mit der C.I.-Nr. 37 080.
• Lösung 2: Entsprechend der sogenannten Kaltlösevorschrift werden, jedoch ohne Formaldehydzusatz, bei50°C 4 kg von Azoic Coupling Component 12 mit der C.I.-Nr. 37 550 mit einer Mischung aus
  
• Badansatz: Man füllt die Lösung 1 mit Wasser von 70°C auf zunächst 140 1 Flotte auf und setzt dieser noch
  

To dye a batch of 230 kg of a stretch cord with the composition of approx. 80% cotton and 20% synthetic polyamide fibers, 200 l of a padding liquor are prepared as follows:

• Solution 1: Dissolve 400 g of oleylmethyl taurine in 70 l of water at 70 ° C. and then 8.8 kg of the cyanamide compound from the diazonium salt of Azoic Diazo Component46 with the CI no. 37 080.
• Solution 2: According to the so-called cold dissolving instructions, but without the addition of formaldehyde, 4 kg of Azoic Coupling Component 12 with the CI no. 37 550 with a mixture of
  
• Bath preparation: Solution 1 is filled with water from 70 ° C to initially 140 1 liquor and this is still set
  

Solution 2 is then stirred into the bath batch and this is filled up with water at 70 ° C. to a volume of 200 liters.

With the padding liquor thus obtained, padding is carried out at 70 ° C. and with 70% liquor absorption (based on the weight of the dry goods) the dyed goods and steams them immediately after padding, without intermediate drying, for 2 minutes at 105 ° C.

aufweist, bei 80°C und 20 Sekunden Tauchdauer der Azofarbstoff auf der Faser entwickelt. Danach wird die Färbung im 2. Kasten bei 70°C mit Wasser gespült, im 3. und 4. Kasten bei 60°C mit einer wäßrigen Flotte unter Zusatz von

und im 5. und 6. Kasten kochend mit 1 g/l Oleylmethyltaurin im wäßrigen Bad geseift. In den Kästen 7 und 8 wird die gefärbte Ware warm (60°C) und kalt mit Wasser gespült und abgespritzt. Danach wird getrocknet.In continuous operation is immediately after steaming by treating the padded goods in the first box of a wide washing machine with an aqueous bath, the

has developed at 80 ° C and 20 seconds immersion of the azo dye on the fiber. The dyeing is then rinsed in the 2nd box at 70 ° C with water, in the 3rd and 4th box at 60 ° C with an aqueous liquor with the addition of

and soaped in the 5th and 6th boxes boiling with 1 g / l oleyl methyl taurine in an aqueous bath. In boxes 7 and 8, the dyed goods are rinsed warm (60 ° C) and cold with water and hosed down. Then it is dried.

A textile material dyed evenly brick red in the proportions of polyamide fiber and cotton is obtained. If the stretch cord is bent up along a rib, the polyamide fiber that appears shows the same color and depth as the cotton pile.

Example 2

• Lösung 1: in 170 1 Wasser von 60°_C 600 g Oleylmethyltaurin und danach 20,4 kg der Cyanamid-Verbindung aus dem Diazoniumsalz von Azoic Diazo Component 2 mit der C.I.-Nr.37 005
• Lösung 2: 6 kg von Azoic Coupling Component 20 mit der C-I.-Nr. 37 530 mit einer Mischung aus
  
  ohne den sonst üblichen Formaldehydzusatz.
• Badansatz: Mit Wasser von 60°C füllt man Lösung 1 auf zunächst 250 1 Flotte auf und setzt dieser noch 600 g eines Sequestriermittels auf Basis von äthylendiamin-tetraessigsaurem Natrium, 3 1 Natronlauge (32,5 %ig) sowie 10 1 Äthanol denat. zu.

For dyeing 400 kg of a Corda fabric containing approx. 20% synthetic polyamide fiber mixed with cotton, 300 l of a padding liquor are prepared. To do this, solve:

• Solution 1: in 170 l of water at 60 ° _C. 600 g of oleylmethyl taurine and then 20.4 kg of the cyanamide compound from the diazonium salt of Azoic Diazo Component 2 with CI No. 37 005
• Solution 2: 6 kg of Azoic Coupling Component 20 with the CI.-Nr. 37 530 with a mixture of
  
  without the usual addition of formaldehyde.
• Bath mixture: With water at 60 ° C, solution 1 is made up to initially 250 1 liquor and 600 g of a sequestering agent based on sodium ethylenediaminetetraacetic acid, 3 1 sodium hydroxide solution (32.5%) and 10 1 ethanol denate are added. to.

Solution 2 is then stirred into the bath batch and this is filled up with water at 60 ° C. to a volume of 300 liters.

With the padding liquor obtained in this way, the cord is padded at 60 ° C and with 70% liquor absorption (from the weight of the goods). Immediately after padding, i.e. without intermediate drying, the damp tissue is steamed for 4 minutes at 102 ° C.

The development of the azo dye on the fiber is carried out by padding the material to be dyed with an 80 ° C. acid solution

In this case, the cord is padded with 100% liquor absorption of the product weight, then subjected to an air passage of 30 seconds at room temperature and the dyeing obtained in this way is rinsed in the first box of a wide-angle washing machine with water at 70 ° C. Finally, the colored goods are soaped in the remaining boxes of the wide-width washing machine in accordance with Example 1.

A full, clear orange dyeing of the cord is obtained with very good tone-on-tone dyeing of polyamide and cotton fibers.

Example 3

• Dazu löst man 3650 g von Azoic Coupling Component 18 mit der C.I.-Nr. 37 520
• mit einer Mischung aus 4 1 Äthanol denat.,
  
• Das ergibt Lösung 1.
• Ferner löst man in 150 1 Wasser von 60°C 340 g Oleylmethyltaurin und
• anschließend 14,5 kg des durch Umsetzung mit Cyanamid stabilisierten Diazoniumsalzes von Azoic Diazo Component 11 mit der C.I.-Nr. 37 085

und setzt dieser Lösung dann ein Gemisch aus

danach die Lösung 1 zu und füllt den Badansatz mit Wasser 60°C auf ein Volumen von 170 1 auf.220 kg of a fabric made of cotton with about 30% synthetic polyamide fiber are to be dyed. With a fleet intake of 65%, 150 1 block fleet are required. In addition, 20 1 are required to fill the chassis. 170 1 padding fleet is therefore prepared as follows:

• To do this, dissolve 3650 g of Azoic Coupling Component 18 with the CI no. 37 520
• with a mixture of 4 1 ethanol denat.,
  
• This results in solution 1.
• Furthermore, 340 g of oleyl methyl taurine and 150 ° C. are dissolved in 150 l of water
• then 14.5 kg of the diazonium salt of Azoic Diazo Component 11 stabilized by reaction with cyanamide and having the CI no. 37 085

and then exposes this solution to a mixture

then add solution 1 and fill the bath with water at 60 ° C to a volume of 170 l.

Now block the fabric with the dyebath prepared in this way at 65% liquor absorption (of the product weight) and 60 ° C and steam it at 102 ° C for 30 seconds without intermediate drying.

The dye material is then dried at 110 ° C for better dye utilization.

The development of the azo dye takes place in the jigger and the aftertreatment at a liquor ratio of 1: 4.

• 11,4 1 Essigsäure (60 %ig),
• 53 kg Kochsalz und
• 8,8 kg Natriumacetat sowie
• 1 kg eines Hilfsmittels auf Basis von mit 20 Mol Äthylenoxid umgesetztem Stearylalkohol, enthaltend 20 % Polyäthylenglykol mit einem Molgewicht von 6000,

aufweist. Danach spült man die Färbung bei 70°C mit Wasser und seift diese 10 Minuten bei 60°C mit einem wäßrigen Bad enthaltend

und dann noch einmal kochend mit Wasser unter Zusatz von

Abschließend spült man die so gefärbte Ware mit Wasser bei 60°C und kalt.It is developed in 2 passages at 80 ° C in an aqueous bath, the

• 11.4 1 acetic acid (60%),
• 53 kg of table salt and
• 8.8 kg of sodium acetate as well
• 1 kg of an aid based on stearyl alcohol reacted with 20 moles of ethylene oxide, containing 20% of polyethylene glycol with a molecular weight of 6000,

having. The dyeing is then rinsed at 70 ° C. with water and soaped for 10 minutes at 60 ° C. using an aqueous bath

and then boiling again with water with the addition of

Finally, the goods so dyed are rinsed with water at 60 ° C and cold.

A full red color covering both types of fibers is obtained.

Note: If the steaming according to the invention is omitted before drying in the present case, the polyamide fiber content gives a significantly lighter color which is not useful in practice.

Example 4

• a) In Wasser von 70°C löst man (bezogen auf das Gesamtvolumen der Klotzflotte)
  
  Man verwendet dazu etwa 2/3 des Gesamtvclumens der zum Färben vorgesehenen Flotte.
• b) Man löst (bezogen auf das Gesamtvolumen der Klotzflotte) 20 g/l von Azoic Coupling Component 2 mit der C.I.-Nr. 37 505

mit der 3-fachen Menge, bezogen auf die Azoic Coupling Component, einer Mischung aus

On a stretch cord made of 80% cotton, 16% synthetic polyamide fiber and 4% polyurethane fiber is one Coloring with 14 g / kg fixed Azoic Coupling Component (naphthol). The following solutions are used:

• a) Dissolve in water at 70 ° C (based on the total volume of the padding liquor)
  
  About 2/3 of the total volume of the liquor intended for dyeing is used for this.
• b) 20 g / l of Azoic Coupling Component 2 with the CI no. (based on the total volume of the padding fleet) are dissolved. 37 505

with 3 times the amount, based on the Azoic Coupling Component, of a mixture of

Solution a is now with

added, the solution b stirred in and filled with water at 60 ° C. to the required total volume of the liquor.

With the padding liquor obtained in this way, the fabric is padded at 60 ° C and 70% liquor absorption (based on the weight of the goods) and then steamed - without drying - at 125 ° C for 30 seconds.

bei 80°C. Die übrige Weiterbehandlung erfolgt wie in Beispiel 1.The dye is developed on a wide washing machine with an aqueous bath with the addition of

at 80 ° C. The rest of the treatment is carried out as in Example 1.

A uniform scarlet dyeing with good tone-on-tone dyeing of cotton pile and the polyamide wound around the polyurethane threads are obtained. The stretch properties of the goods are not affected in any way.

Example 5

Dye 270 kg of a mixture of polyamide fiber and cotton in a ratio of 20:80. With a planned fleet intake of 70%, 190 1 block fleet + 30 1 chassis filling = 220 1 fleet are required.

• a) 4,4 kg von Azoic Ccupling Component 12 mit der C.I.-Nr. 37 550 mit einer Mischung aus
  
• b) in 100 1 Wasser 70°C
  
  und setzt b) zu einem Gemisch aus
  

You solve

• a) 4.4 kg of Azoic Ccupling Component 12 with the CI no. 37 550 with a mix of
  
• b) in 100 l of water at 70 ° C
  
  and exposes b) to a mixture
  

Then a) is stirred into b) and the bath mixture is filled with water at 70 ° C. to a total volume of 220 l.

After padding the textile goods at 70 ° C and 70% liquor absorption (by the weight of the goods), they are steamed for 3 minutes at 102 ° C while wet and then the dye is developed with the same additives as in Example 1 and the dyed goods are post-treated.

A uniform, full wine red fermentation of both types of fibers is obtained. The color tone on the polyamide fiber largely corresponds to that on the cotton.

Claims (4)

1. Process for continuous or semi-continuous, single-bath, uniform tone-on-tone dyeing of textile fabrics or knitted fabrics from mixtures of cellulose fibers and synthetic polyamide fibers according to a block dyeing technique with a coupling component and a diazo component in the form of a stabilized diazonium compound on the fiber are insoluble azo dyestuffs produced by the _F ARB material components applied together under alkaline conditions and dyestuff development is caused by the action of acid, characterized in that there is used as the diazo component a water-soluble diazoamino compound from a diazotized, aromatic or heterocyclic amine and cyanamide, that both dye components dissolved in an aqueous, alcohol-containing liquor at temperatures of 60 ° to 70 ° C blocks on the textile and that this primer immediately after padding and before the release of the diazonium compounds g and coupling dampens necessary acid treatment without intermediate drying. 2. The method according to claim 1, characterized in that the textile material is steamed for 30 seconds to 5 minutes, preferably up to 2 minutes. 3. The method according to claim 1 or 2, characterized in that the textile material is steamed at temperatures of 101 ° to 107 ° C, preferably at 103 ° to 105 ° C. 4. The method according to claim 1 or 2, characterized in that the textile material is damped at Temperaturcn from 120 ° to 135 ° C.