EP0014384B1 - Process for dyeing in one single bath of mixtures of cellulose fibres and synthetic polyamide fibres with azo developing dyestuffs - Google Patents

Description

The present invention relates to a method for single-bath, uniform tone-on-tone dyeing of textile fabrics or knitted fabrics from mixtures of cellulose fibers and synthetic polyamide fibers by the exhaust method with insoluble azo dyes produced on the fiber from the coupling component and diazo component in the form of a stabilized diazonium compound in that the dye components are applied at least partially in succession under alkaline conditions and the dye development is brought about by the action of acid.

The ice dye technique that has long been introduced for dyeing textile articles with so-called development dyes is based on the principle of assembling the insoluble dye on the fiber from two relatively small, soluble and well-diffusing sections.

Within the scope of this field of work, DE-PS 1 262 957 describes an exhaust process for the production of water-insoluble azo dyes on cellulose fibers, which involves the use of a mixture of a coupling component (hereinafter referred to as "naphthol") with a stabilized and not readily couplable diazonium Connection (hereinafter referred to as "diazo salt"). Diazoamino compounds which can be obtained by reacting the diazotized amine with cyanamide and which, following the pull-up phase under acidic conditions, are re-formed into the couplable diazonium compound and used for coupling with the naphthol are used as such a “diazo salt”. to be brought. It can be seen that this process, since it brings "naphthol" and "diazo salt" together from a bath onto the fiber and does not require diazotization on the fiber, is easier to use than the classic dyeing method on cotton, in which coupling and diazo component must be applied from separate baths. For the implementation in practice, this pull-out technique is explained in the information leaflet of the Hoechst Aktiengesellschaft "Technical Council from Hoechst" / Textile No. 164 ¹ .

Furthermore, a process for dyeing polyamide fibers is known from Melliand Textile Reports 40/1959, Issue 3, pages 295-300, according to which an alkaline solution of “naphthol” and a water-insoluble, by triazine formation of the diazotized amine are jointly applied to the textile material from an aqueous liquor applied a secondary amine stabilized diazonium compound in the exhaust process. The elimination of the stabilizing moiety and dye coupling of the two components is then ^g by treatment with a fresh, hot sulfuric acid containing DEVELOPMEN SBAD brought about.

For the dyeing of mixtures of such polyamide fibers and cellulose fibers using the ice dye technique, Melliand Textile Reports, loc. cit. It is recommended to combine the above-described extraction process with the joint use of "naphthol" and the stabilized, water-insoluble diazonium compound mentioned there with the traditional dyeing method for 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 coupling-capable diazonium -Connection - with the same aromatic amine as the base if possible - generated.

Not only is the very cumbersome and complicated nature of the dyeing processes opposed to the widespread use of the methods discussed above in practice, there are also relatively large amounts of dye that have to be used for this. A very significant disadvantage, however, is the high wastewater pollution caused by the various dyeing and developing liquors not used in these known methods. In addition, there is at least twice as much water consumption for the various essential rinsing processes.

In recent times, a textile article made of polyurethane threads covered with synthetic polyamide threads and cotton - referred to in practice 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.

The present invention is based on the object of eliminating the abovementioned disadvantages in the dyeing process using coupling and diazonium components from ice-dye technology, thereby achieving a waste water pollution which is at least halved and bringing about a much lower water consumption, in which case mixtures of cellulose fibers and synthetic polyamide fibers are to be dyed in a single operation, both fiber parts simultaneously and in a matching shade.

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 by treating the textile material at from 65 ° to 75 ° C. with an aqueous liquor which contains the dissolved diazo component and optionally containing a protective colloid, then this liquor together with the primed textile at temperatures of 30 ° to 45 ° C. cools down and further treated at the reduced temperature, with the dissolved coupling component being added in portions at the same time during these two phases of the dyeing operation, and the acid treatment required for releasing the diazonium compound and coupling being carried out without changing the liquor.

• Da aufgrund der geringeren Quellbarkeit von hydrophoben Fasern im Vergleich zu Baumwolle-Polyamidfasern, auch als Bestandteil von Mischungen mit Cellulosefasern, in Form von Geweben und Gewirken entsprechend den herkömmlichen Praktiken immer bei Kochtemperatur gefärbt werden, war es überraschend, daß bei diesem neuen Verfahren auf Basis der Eisfarbentechnik, bei welchem die Flotte auf maximal etwa 75°C erhitzt wird, volle Färbungen resultieren. Desgleichen hat der Fachmann nicht vorhersehen können, daß man unter den erfindungsgemäßen Bedingungen vollkommen egale Färbungen auf dem Polyamidfaseranteil erhält, denn nach bisheriger Ansicht vermögen für dieses synthetische Fasermaterial geeignete Farbstoffe nur bei Kochtemperatur optimal zu migrieren und auf diese Weise die vorhandene Neigung zu Unregelmäßigkeiten zufriedenstellend auszugleichen.

According to the present invention, with the aid of a special temperature control during the course of the dyeing process in connection with a portionwise addition of the amount of coupling component required for the dyeing to the cyanamide-stabilized diazonium compound in the dye bath, both fiber portions are colored tone-on-tone. The dyeing result achieved in the course of the measures of the method according to the invention could not, however, be readily expected:

• Since, due to the lower swellability of hydrophobic fibers compared to cotton-polyamide fibers, also as a component of blends with cellulose fibers, in the form of woven and knitted fabrics, dyeing is always carried out at cooking temperature in accordance with conventional practices, it was surprising that this new process based on the ice color technique, in which the liquor is heated to a maximum of about 75 ° C., results in full colorations. Likewise, the person skilled in the art could not have foreseen that completely level dyeings on the polyamide fiber content would be obtained under the conditions according to the invention, because, according to the previous view, dyes suitable for this synthetic fiber material can only migrate optimally at cooking temperature and in this way satisfactorily compensate for the tendency to irregularities .

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. The new dyeing process proceeds as follows:

It is recognized, an aqueous dye liquor which contains 5 to 7 cm ^3/1 sodium hydroxide solution (32.5% pure), from 0 to 2 g / I of a protective colloid based on sulfite waste liquor, which is generally necessary for reasons of bath stability, and from 10 to Contains 30 g / I sodium chloride or sodium sulfate. In this bath, the amount required for the staining is added a solution of the stabilized with cyanamide diazonium compound ( "diazo salt"), the previously added for reasons of solubility even 0.2 to 0.4 g / I Oleylme ^t hyltaurin. have been. Finally, depending on the combination of “naphthol” and “diazo salt” used, this bath is added with a third to two thirds of the total amount of the coupling component released according to the cold dissolving instructions. The bath prepared in this way already has a temperature of 65 ° to 75 ° C., preferably 70 ° C., from the dissolving process or is optionally heated to this temperature if it should have dropped below it by added solutions etc.

The fiber material is dyed with this liquor for 20 minutes at the set temperature of 65 ° to 75 ° C., then the liquor is allowed to cool down to temperatures of 30 ° to 45 ° C. together with the textile material contained therein. This process can be accelerated by adding cold water, in which case the dye bath of the first stage is not prepared with the full amount of liquor from the outset. In general, one is satisfied with a reduced dyeing bath temperature, which is 35 ° to 40 ° C, because firstly the cooling process does not take so long and, moreover, it does not require as much energy. When the desired temperature is reached, the remaining amount of coupling component is added and the goods are dyed again for 20 minutes at the now lower temperature. This latter process is the actual primer for the cellulose fiber content.

According to the present invention, it is in principle also possible to let the textile material run for a short time with the liquor without the coupling component at the dyeing temperature and only then to add the coupling component, whereupon the dyeing process is continued in the manner described above.

At the end of the aforementioned second phase of the dyeing operation, the pull-out bath will be given the amount specified for the combination of "naphthol" and "diazo salt" in the information leaflet of the Hoechst Aktiengesellschaft "Technical Council from Hoechst", textile No. 164 ¹ , without changing the fleet Acetic acid is added and the textile material is treated again under this acidic condition for 20 to 30 minutes at this temperature. During this time, the hitherto stabilized diazonium compound: and the coupling of the development dye on the fiber take place. The goods are then soaped and finished as usual. The result is brilliant and genuine dyeings on the textile material, with both fiber parts being dyed in completely the same shade.

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.

• Es sind dies vor allem die
  • Azoic Coupting Companent 23
• mit der C.I.-Nr. 37555
  • Azoic Coupling Component 28
• mit der C.I.-Nr. 37541
  • Azoic Coupling Component 32
• mit der C.I.-Nr. 37580
  • Azoic Coupling Component 13
• mit der C.I.-Nr. 37595
  • Azoic Coupling Component 25

mit der C.I.-Nr. 37590
und mit gewissen Einschränkungen Azoic Coupling Component 12
mit der C.I.-Nr. 37550Of the "naphthols", the medium to highly substantive products are preferably used for the exhaust process.

• Above all, they are
  • Azoic Coupting Companent 23
• with the CI no. 37555
  • Azoic Coupling Component 28
• with the CI no. 37541
  • Azoic Coupling Component 32
• with the CI no. 37580
  • Azoic Coupling Component 13
• with the CI no. 37595
  • Azoic Coupling Component 25

with the CI no. 37590
and with certain restrictions Azoic Coupling Component 12
with the CI no. 37550

The new process can be used for any type of blended fabrics and knitted 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 chemicals relates to “percent by weight”.

example 1

• 6 cm³ Natronlauge (32,5%ig),
• 2 g eines Schutzkolloids auf Basis Ligninsulfonat und
• 20g Kochsalz,

die Temperatur beträgt 70°C. In diese Flotte werden

• 7,5 g/I des durch Umsetzung mit Cyanamid stabilisierten Diazoniumsalzes von Azoic Diazo Component 32 mit der C. I.-Nr. 37090, und
• 0,3 g/l Oleylmethyltaurin,

in der achtfachen Menge Wasser von 65°C gelöst, eingegossen und gut verrührt.In a jet dyeing machine, 50 kg of a cotton-polyamide fiber blended fabric with a polyamide fiber content of 30% are to be dyed using the exhaust method. The 600 I dye liquor required for this (liquor ratio 1:12) contains 1 liter of water

• 6 cm ³ sodium hydroxide solution (32.5%),
• 2 g of a protective colloid based on lignin sulfonate and
• 20g table salt,

the temperature is 70 ° C. Into this fleet

• 7.5 g / l of the diazonium salt of Azoic Diazo Component 32 stabilized by reaction with cyanamide and having the CI no. 37090, and
• 0.3 g / l oleyl methyl taurine,

dissolved in eight times the amount of water at 65 ° C, poured in and stirred well.

• 0,75 g/l von Azoic Coupling Component 28 mit der C. I.-Nr. 37541,

After that, the fleet approach is also added

• 0.75 g / l from Azoic Coupling Component 28 with CI no. 37541,

• 1,9 cm³ Äthanol denat.,
• 0,36 cm³ Natronlauge (32,5%ig) und
• 1,5 cm³ Wasservon40°C

added, which according to the so-called cold dissolving rule (no formaldehyde addition) with a mixture of

• 1.9 cm ³ ethanol denat.,
• 0.36 cm ³ sodium hydroxide solution (32.5%) and
• 1.5 cm ^{3 of} water at 40 ° C

have been resolved.

• 0,75 g/I von Azoic Coupling Component 28 mit der C. I.-Nr. 37541

in gelöster Form (wie oben) zugegeben und das Mischgewebe wird weitere 20 Minuten bei der erniedrigten Temperatur behandelt.The possibly cooled bath is now heated to 70 ° C and held at this temperature for 20 minutes. During this time, the textile material is treated with the liquor prepared in the above manner. The fleet is then cooled to 35 ° C. together with the goods. When this temperature is reached, the bath again

• 0.75 g / I from Azoic Coupling Component 28 with CI no. 37541

added in dissolved form (as above) and the mixed fabric is treated for a further 20 minutes at the reduced temperature.

• 12 cm³/l Essigsäure (60%ig)

zu und behandelt das Färbegut nochmals 20 Minuten bei der eingestellten Temperatur von 35° C unter den jetzt sauren Bedingungen. Zum Abschluß wird die so erzeugte Färbung geseift und wie üblich fertiggestellt.Then add the primer liquor for dye development

• 12 cm ³ / l acetic acid (60%)

and treated the material to be dyed again for 20 minutes at the set temperature of 35 ° C under the now acidic conditions. Finally, the dyeing is soaped and finished as usual.

As a result of the treatment described, the blended fabric on both fiber components is colored completely evenly in a strong red.

Example 2

• 12 g/l des durch Umsetzung mit Cyanamid stabilisierten Diazoniumsalzes von Azoic Diazo Component 11 mit der C. I.-Nr. 37085, und
• 0,3 g/I Oleylmethyltaurin,

in der achtfachen Menge Wasser von 65°C gelöst, eingegossen und gut verrührt.As described in Example 1, 900 l of dye liquor (liquor ratio 1:15) are used for dyeing 60 kg of stretch cord from a polyamide fiber / cotton mixture in which the polyamide fiber content is 10%. The temperature is 73 ° C. In this fleet are here

• 12 g / l of the diazonium salt of Azoic Diazo Component 11 stabilized by reaction with cyanamide and having the CI no. 37085, and
• 0.3 g / l oleyl methyl taurine,

dissolved in eight times the amount of water at 65 ° C, poured in and stirred well.

• 0,5 g/I von Azoic Coupling Component 32 mit der C. I.-Nr. 37580

zugesetzt, die nach der sogenannten Kaltlösevorschrift (der Formaldehydzusatz unterbleibt) mit einer Mischung aus

• 1 cm³ Äthanol denat.,
• 0,25 cm³ Natronlauge (32,5%ig) und
• 0,5 cm³ Wasser von 60° C

gelöst worden sind.After that, the fleet approach is also added

• 0.5 g / I from Azoic Coupling Component 32 with CI no. 37580

added, which according to the so-called cold dissolving rule (no formaldehyde addition) with a mixture of

• 1 cm ^{3 of} ethanol denat.,
• 0.25 cm ³ sodium hydroxide solution (32.5%) and
• 0.5 cm ^{3 of} water at 60 ° C

have been resolved.

• 0,5 g/1 von Azoic Coupling Component 32 mit der C. I.-Nr. 37580

in gelöster Form (siehe oben) zugegeben und der Stretchcord wird weitere 20 Minuten bei der erniedrigten Temperatur behandelt.With the liquor prepared in the above manner, the textile material is treated for 20 minutes and at a temperature of 72 ° C. The fleet and the goods are then cooled to 35 ° C. When this temperature is reached, the bath again

• 0.5 g / 1 of Azoic Coupling Component 32 with the CI no. 37580

added in dissolved form (see above) and the stretch cord is treated for a further 20 minutes at the reduced temperature.

• 12 cm³/1 Essigsäure (60%ig)

zu und läßt die jetzt sauer eingestellte Flotte 20 Minuten bei 35°C auf das Färbegut einwirken. Zum Abschluß wird die so erzeugte Färbung wie üblich geseift und fertiggestellt.The dye bath is then added to the pull-out bath

• 12 cm ^3/1 acetic acid (60%)

and allows the now acidic liquor to act on the material to be dyed at 35 ° C. for 20 minutes. Finally, the dyeing so produced is soaped and finished as usual.

After drying, the stretch cord is colored completely evenly in a strong red on both fiber parts of the mixture.

Example 3

• 0,3 g/I des durch Umsetzung mit Cyanamid stabilisierten Diazoniumsalzes von Azoic Diazo Component 5 mit der C. I.-Nr. 37125, und
• 0,2 g/I Oleylmethyltaurin
• in der achtfachen Menge Wasser von 65°C gelöst, eingegossen und gut verrührt.

40 kg of cellulose-polyamide fiber knitwear with a polyamide fiber content of 20% are dyed in 10001 dyeing liquor according to Example 1 (liquor ratio 1:25) on a reel runner. In this case, in this fleet

• 0.3 g / l of the diazonium salt of Azoic Diazo Component 5 stabilized by reaction with cyanamide and having the CI no. 37125, and
• 0.2 g / l oleyl methyl taurine
• dissolved in eight times the amount of water at 65 ° C, poured in and stirred well.

• 1 g/I von Coupling Component 28 mit der C.I.-Nr. 37541

zugesetzt, welches man nach der sogenannten Kaltlösevorschrift (jedoch ohne Formaldehyd) mit einem Gemisch aus

• 2,5 cm³ Äthanol denat.,
• 0,5 cm³ Natronlauge (32,5%ig) sowie
• 2 cm³ Wasser von 40° C

After that, the fleet approach is also added

• 1 g / I from Coupling Component 28 with CI no. 37541

added, which is made according to the so-called cold dissolving procedure (but without formaldehyde) with a mixture

• 2.5 cm ³ ethanol denat.,
• 0.5 cm ³ sodium hydroxide solution (32.5%) and
• 2 cm ^{3 of} water at 40 ° C

has brought in solution.

• 0,5 g/I von Azoic Component 28 mit der C.I.-Nr. 37541

in gelöster Form (analog oben) zugefügt und das Gewirke wird weitere 20 Minuten bei der erniedrigten Temperatur behandelt.After heating to 70 ° C, the textile material is treated with this liquor for 20 minutes, after which the liquor and the goods are cooled together to 35 ° C. When this temperature is reached, the bath again

• 0.5 g / l of Azoic Component 28 with CI no. 37541

added in dissolved form (analog above) and the knitted fabric is treated for a further 20 minutes at the reduced temperature.

• 12 cm³/1 Essigsäure (60%ig)

zu und setzt das Färbegut 20 Minuten bei 35°C dem jetzt eingestellten sauren Milieu aus. Bei diesem letzterwähnten Schritt wird der Farbstoff auf den beiden Faserkomponenten entwickelt. Die in dieser Weise erhaltene Färbung wird zum Abschluß geseift und wie üblich fertiggestellt.Without changing the fleet, you then add to the pull-out bath

• 12 cm ^3/1 acetic acid (60%)

and exposes the material to be dyed to the acidic medium now set at 35 ° C for 20 minutes. In this latter step, the dye is developed on the two fiber components. The dyeing obtained in this way is soaped at the end and finished as usual.

The fabric treated according to the above regulation is dyed completely evenly in a deep red shade on both fiber components.

Claims (3)

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 the exhaust method 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 applied, at least partly in successive manner, under alkaline conditions and dyestuff development is caused by the action of acid, which process comprises using as the diazo component a water-soluble diazoamino compound obtained from a diazotized, aromatic or heterocyclic amine and cyanamide, treating the textile goods at temperatures ranging of from 65° to 75° with an aqueous liquor containing the dissolved diazo component and a protective colloid, subsequently cooling down said liquor together with the impregnated textile good to temperatures ranging of from 30° to 45°C and further treating the same at the said decreased temperature, while simultaneously adding in portions the dissolved coupling component in the course of the both phases of the dyeing operation performed at the different temperature ranges, and finally effecting the acid treatment, which is necessary for liberating the diazonium compound and coupling, without change of the liquor.

2. A process as claimed in claim 1, wherein the dissolved coupling component is added to the bath at about 70°C in an amount involving ¹/₃ to ²/₃ the volume of the required total amount thereof, and the residual amount thereof is added to the cooled liquor.

3. A process as claimed in Claim 1 or 2, wherein the first phase of the dyeing operation is carried out at temperatures ranging of from 65° to 70° C, and the second phase is carried out at temperatures ranging of from 35° to 40° C.