EP0198417A2 - Process for level dyeing cellulosic fibrous materials between the ends using azoic ingrain dyes - Google Patents

Abstract

1. A process for dyeing textile sheet materials, or textile articles made up in sheet form, made of cellulose fibers or mixtures thereof with synthetic fibers with a water-insoluble azo dye formed on the fiber from a coupling component and a diazo component in the form of a stabilized diazoamino or tetrazoamino compound or a diazotate, without tailing, by applying the dyeforming components continuously and together to the textile material by direct transfer from an aqueous liquor containing these substances under alkali conditions without dipping the textile material in said liquor and bringing about subsequent dye formation by the action of an acid, which comprises applying the liquor which contains the two dye-forming components to the specific area envisaged on the substrate surface by a minimum addon technique which ensures uniform application of small amounts of liquid.

Description

The present invention relates to the dyeing of textile fabrics or web articles made from cellulose fibers or mixtures thereof with synthetic fibers, with coupling component and diazo component in the form of a stabilized diazoamino or tetrazoamino compound or a diazotate on the fiber, by the Dye-forming components are applied continuously and together by direct transfer from an aqueous liquor containing these substances under alkaline conditions to the goods without dipping the textile goods therein, and the subsequent dye development is brought about by the action of acid.

For the continuous dyeing of cellulosic fiber materials with azo developing dyes, the foulard technique has primarily been used so far. In the case of a liquor application of the dye-forming components by padding, a solution of the same is mechanically pressed (impregnated) onto the spread web by passing the substrate to be dyed through a bath (chassis) filled with treatment liquor and then squeezed off from the excess liquor.

According to the methods introduced in practice, when dyeing with water-insoluble azo dyes produced on the fiber, it is customary nowadays to first impregnate the textile material with the dissolved coupling component (azoic coupling component) as a so-called "primer" and only then in a further operation to form the To effect developing dye by coupling. Such a primer consists essentially of the alkaline solution of a coupling component (hereinafter also referred to briefly as "naphthol"), in particular of an arylamide of 2-hydroxy-3-naphthoic acid or an arylamide of ketocarboxylic acids. The dye is developed by treating the previously mentioned primer with a solution of a diazonium compound (Azoic Diazo Component) under acidic conditions.

However, if non-coupling-capable diazonium compounds are used as diazo components in this known two-stage dyeing process, "naphthol" and diazonium compound can be applied to the goods from a common bath in the course of the measures described. According to the way explained, the implementation of the dyeing operation in a continuous manner can be considered. In the case of dyeing textile goods in high batches, such single-bath process techniques have so far failed because the more or less pronounced influence on the color tone ^* by the substantivity of "naphthol" has had a negative effect on the so-called "end flow" of the dyed goods. Any kind of technical trick in the process flow, be it the weakening of the batch or the reinforcement of the batch, has to fail due to the special nature of the conditions prevailing in a continuous one-bath process of the type mentioned. This circumstance consequently also means that the dyeing processes claimed in the German patent specification DE-C-29 02 977 as well as in the German laid-open documents DE-A-26 06 905 and DE-A-19 15 390 are affected by the phenomenon in question and in Use of large quantities of goods results in a visible end sequence. The occurrence of substantivity in "naphthol" thus makes the use of these conventional methods according to the prior art practically impossible, provided that it concerns the dyeing of large crops.

^* ) and the color depth

Now, however, it means for the person skilled in the art a fixed fact of experience that only a few, low substantive "naphthols" are available for the padding of textile material webs in the conventional way, in order to solve the previously spread difficulties, for which the problem of the end sequence is somewhat empirical dominates. The larger number of medium to highly substantive "Napthole", however, can not be used for normal dyeing on the foulard, because the negative influence of the dyeing result achieved by the end sequence can otherwise not be handled without special measures to compensate.

The purpose of the present invention is therefore to develop a process which succeeds in eliminating or circumventing the effect of the substantivity of the "naphthols", so that the single-bath continuous operation discussed above without impairing the color tone through the end drain can be realized. Such a continuous process should neither include intermediate drying or necessary intermediate storage of the goods loaded with the dye-forming components, nor should special textile auxiliaries be required for wet-on-wet work. ^* ) and the color depth

This object is achieved in that the impregnation of the liquor containing the two dye-forming components next to one another is carried out at the intended location on the substrate surface by means of an application measure which effects the uniform application of small amounts of liquid (minimal application) and then for the release of the coupling-capable diazonium compound and coupling in proceeds in the usual way.

Preferably, in the course of the minimum contract according to this new method fleet intakes by the Tex _- tilgut in the range between 15% and 50% (based on the weight of the dry goods).

When carrying out the claimed process, it is possible to eliminate the harmful influence of the substantivity of "naphthols" present in the primer liquors as coupling component on the quality of the continuous dyeings with azo developing dyes and thus that of conventional block application (impregnation and squeezing) ) to counter the "naphthols" constantly occurring difficulties, which are connected with the end sequence caused by the substantivity with regard to the lack of uniformity in the shade of the colorings produced in this way.

In addition to the advantage of the deactivated substantivity, there is another advantage that the "naphthol" does not have to be applied hot according to the invention. Such a liquor can also be thickened, for example by adding glue, so that a very precise application of dye components can be carried out, which means that no excess dye is used in this way; the wastewater pollution is therefore much lower.

For the feasibility of the present invention, it has been found to be essential that the application takes place through direct transfer of the treatment liquor to be applied without dipping the material to be treated therein. Due to the anchoring of the freshly arriving fleet in the immediate area of the application points (similar to printing), as a result of the typical type of impregnation process combined with intercapillary suction forces, there is no displacement of any already present in the fiber material (not in excess) Moisture triggered and can thus also result in no movement of the fleet due to relocation within the goods. According to the invention, only the treatment agent is evenly distributed in the total liquid on the fiber, so that the substantivity of the "naphthols" only comes into play on the spot. Such behavior can therefore no longer give rise to an "additional" undressing of the "naphthol" as occurs during a diving operation.

Devices which guarantee a so-called "minimum order" within the meaning of the previously discussed reservation in terms of fleet expansion and in terms of fleet intake quantities within the above-mentioned limits of only 15% to 50% of the weight of the items to be treated (compared to a minimum of 50% in previous padding application processes) are in recently in retail. Examples of this are described in German Offenlegungsschrift DE-A-29 11 166, German Patent DE-C-30 04 941 and DE-C-30 33 478 and in European Patent EP-B-00 47 484.

Now, however, it is no longer new for a person skilled in the art that in the case of splashing, there is a similar functional principle for the application of the liquor by applying the treatment agent to the textile material by means of the same application roller under the machine conditions there. Although a dipping process does not play a role on this basis either, there are - as has surprisingly been found - different specific conditions depending on the different apparatus arrangement, but which are not suitable for a uniform and targeted method corresponding to the method according to the invention Minimum dosage of the fleet order over the length and width of the web. Rather, there is a fleet wedge between the roller and the goods during the finishing process trained, which is squeezed off in the course of the movement of the goods towards the two side edges of the textile web, so that the fleet, depending on its drift, finds the occasionally unevenly longer pull out than elsewhere on the width of the goods and in the event of a dyeing process as a result - under one Diving process comparable requirements - the so-called page drain sets in color.

Furthermore, a method for the direct minimal application of dyes or finishing agents containing liquors in the form of foam on textile webs is already known from the German designations DE-B-22 14 377 and DE-B-24 02 353, the application amount being too applying, foamed fleet over the height of the goods surface, for example foam layer applied by means of nozzles, i.e. the foam volume is controlled. This foam application technique without dipping is, however, a completely different principle of metering, which cannot be compared with the measures used for this purpose according to the invention.

Although there are conditions according to the two previously discussed methods based on the principle of splashing or applying foam, such as are also used in the case of the present invention, it must be assumed on the basis of the concrete statements made in the literature regarding this state of the art that these known ways of working have been designed with the intention of reducing the amount of liquor to be applied and, consequently, a reduction in the drying capacity required. A technical teaching that the substantivity of treatment agents can also be switched off with the aid of these conventional process technologies has so far not been imparted anywhere. It is solely the merit of this invention that Utilization of the minimum order, which is usually carried out in direct transmission without dipping the material to be treated, as a way of countering or counteracting the consequential effects of the substantivity of "naphthols" so that the same colorations result.

The process according to the invention is carried out, for example, by impregnating raw or ready-to-dye cellulose fiber fabric with an alkaline, thickened solution which contains a more or less substantive coupling component, a stabilized, non-coupling diazonium compound in the form of a diazoamino or tetrazoamino compound or an antidiazotate and optionally also contains a dispersant and / or a wetting agent. The above-described impregnation liquor containing the dye-forming components can advantageously also be used in the form of a fine-pored foam. Due to the inherent consistency of such foams, a certain amount of the thickener can be saved in this variant. It is now the characteristic feature of the present invention that this liquor application is carried out without diving using a minimal application device. The stabilized diazonium compound is converted into the couplable form by subsequent treatment of the textile webs, which have been pre-primed in accordance with the process, with acidic agents, which either consist of acidic steaming or an acid passage, so that a pH value between 3 and 6 is established on the goods coupling occurs and with it the formation of dye on the fiber. Finally, the coloring thus produced is then post-treated and finished in the manner customary in accordance with the ice color technique.

Suitable coupling components in the process according to the invention are predominantly those which have a low to medium substantivity towards cellulose fibers have. Suitable compounds are, for example, 2,3-hydroxynaphthoylaminobenzene, 1- (2 ', 3'-hydroxynaphthoylamino) -2-methylbenzene, 1- (2', 3'-hydroxynaphthoylamino) -2-methoxybenzene, 1- (2 ', 3'-hydroxynaphthoylamino) -3-nitrobenzene, 1- (2 ', 3'-hydroxynaphthoylamino) -4-methoxybenzene, 1- (2', 3'-hydroxynaphthoylamino) -2-methyl-4-methoxybenzene, 1- (2 ', 3'-hydroxynaphthoylamino) -2,5-dimethoxybenzene, 1- (2', 3'-hydroxynaphthoylamino) -2-methyl-4-chlorobenzene, 1- (2 ', 3'-hydroxynaphthoylamino) -2-methoxy- 5-chlorobenzene, 1- (21,31-hydroxynaphthoylamino) -2,4-dimethoxy-5-chlorobenzene, 1- (2 ', 3'-hydroxynaphthoylamino) naphthalene, 4,4'-bis-acetoacetylamino-3,3 '-dimethyldiphenyl or 1-acetoacetylamino-2,5-dimethoxy-4-chlorobenzene.

Coupling components with higher substantivity, for example 2- (2 ', 3'-hydroxynaphthoylamino) naphthalene, 1- (2', 3'-hydroxynaphthoylamino) -2-methoxy-4-chloro-5-methylbenzene, 1- (2 ', 3'-hydroxynaphthoylamino) -2,5-dimethoxy-4-chlorobenzene, 2- (2 ', 3'-hydroxynaphthoylamino) -3-methoxy-diphenylene oxide or 1- (2'-hydroxycarbazole-3'-carboylamino) -4- Chlorobenzene can also be used in the process according to the invention. In contrast to other order processes, special measures that counteract substantivity can be dispensed with.

As Diazoamino- or Tetrazoaminoverbindungen those from diazotized aromatic or heterocyclic mono-or diamines, such as diazotized chloroanilines, Dichloranilinen, Chlortoluidinen, Chloranisidinen, nitroanilines, Nitrotoluidinen, Nitroanisidinen, Nitroxylidinen, Nitrophenetidinen, Cyantoluidinen, Cyananisidinen, Aminobenzolsulfonsäureamiden, Aminobenzolcarbonsäureamiden, Aminophenylalkyl-, aryl or aralkyl sulfones, aminodiphenyl ethers, trifluoromethylanilines, monoacylated phenylenediamines, aminoazobenzenes, 4,4'-diaminodiphenyls or amino carbazoles, and primary or secondary aliphatic or aromatic amines, for example N-alkylated aliphatic aminocarboxylic acids or aminosulfonic acids, N-alkylated aromatic aminocarboxylic acids or aminosulfonic acids, aminosulfocarboxylic acids or cyanamide.

Suitable antidiazotates are likewise those compounds obtainable from the above-mentioned primary aromatic amines.

The chemical compounds previously described for the production of azo development dyes by the new process are described in COLOR INDEX, 3rd edition 1971 and additions in 1975 under the term "azoic coupling component" and in the case of the amines on which the stabilized diazonium compounds are based, as "azoic diazo component" listed.

Suitable dispersants which can also be used in the alkaline impregnation bath are the compounds customary in ice color technology, for example condensation products from higher molecular weight fatty acids and protein degradation products, condensation products of formaldehyde with naphthalenesulfonic acids or purified sulfite cellulose waste liquor.

Alkyl aryl sulfonates are preferably used as wetting agents.

The acidic compounds in the development bath are organic acids, for example formic acid, acetic acid, propionic acid, or acidic salts, for example monosodium phosphate. To set a pH value on the goods that is favorable for the formation of dyes, it may also be expedient to use a mixture of a salt of an organic acid and an organic acid, for example a mixture of sodium acetate and acetic acid.

The process according to the invention can be applied to the known cellulosic fibers and mixtures of synthetic fibers, e.g. Polyester fibers, and cellulose fibers are used. In this context, the cellulose fibers are native fibers such as flax, hemp, linen and cotton, or regenerated fibers such as viscose, rayon and modal fibers.

The percentages given in the examples below are percentages by weight and relate to the weight of the dry goods in the case of liquor absorption.

example 1

• Lösung 1): Man löst in 100 1 Wasser von 70°C 800 g Oleylmethyltaurin und danach 13,2 kg der Diazoaminoverbindung aus diazotierter Azoic Diazo Component 46 mit der C.I.-Nr. 37 080 und Cyanamid.
• Lösung 2): Entsprechend der sogenannten Kaltlösevorschrift werden, jedoch ohne Formaldehydzusatz, bei 50°C 6 kg von Azoic Coupling Component 12 mit der C.I.-Nr. 37 550 mit Hilfe einer Mischung aus
  
• Badansatz): Man füllt die Lösung 1) mit Wasser von 20°C auf zunächst 150 1 Flotte auf und setzt dieser noch
  

To dye a batch of 230 kg of cotton nettle fabric, 200 liters of an aqueous liquor are prepared as follows:

• Solution 1): 800 g of oleylmethyl taurine and then 13.2 kg of the diazoamino compound from diazotized Azoic Diazo Component 46 with the CI no. 37 080 and cyanamide.
• Solution 2): According to the so-called cold dissolving instructions, but without the addition of formaldehyde, 6 kg of Azoic Coupling Component 12 with the CI no. 37 550 using a mixture of
  
• Bath preparation): The solution 1) is filled with water from 20 ° C to initially 150 1 liquor and this is still set
  

Then solution 2) is stirred into the bath batch and this is filled up with water at 70 ° C. to a total volume of 200 l.

With the liquor thus produced, the dyed material is impregnated by direct transfer without dipping it at 25 ° C. and with a liquor absorption of 40% using a device for minimal application described in European Patent EP-B-0 047 484.

• 80 ml/l Essigsäure (50 %ig) und
• 50 g/1 Kochsalz

enthält, und einen Luftgang von 20 Sekunden Dauer anfügt. Heißes Spülen mit Wasser und darauffolgendes Seifen des gefärbten Textilmaterials schließen den Färbevorgang ab.The dye development is then carried out through an acid passage, the product thus treated being continuously passed through an 80 ° C. hot, aqueous development bath which

• 80 ml / l acetic acid (50%) and
• 50 g / 1 table salt

contains, and adds an air passage of 20 seconds duration. Hot rinsing with water and subsequent soaping of the dyed textile material complete the dyeing process.

There is a scarlet color on the fabric.

Example 2

• Eine Mischung aus
  • 20 g von Azoic Coupling Component 17 mit der C.I.-Nr. 37 515 und
  • 60 g des Antidiazotates aus diazotierter Azoic Diazo Component 10 mit der C.I.-Nr. 37 120 wird in einem Gemisch aus
    

An aqueous impregnating liquor of the following composition is used for the continuous dyeing of cotton twill:

• A mix of
  • 20 g of Azoic Coupling Component 17 with the CI no. 37 515 and
  • 60 g of the antidiazotate from diazotized Azoic Diazo Component 10 with the CI no. 37 120 is made up of a mixture
    

With a minimal application device as in Example 1, this liquor is applied to the fabric at 20 ° C. and a liquor application of 40% by direct transfer without dipping it.

enthält. Daraufhin wird das gefärbte Textilgut einem kurzen Luftgang unterworfen, sodann zunächst mit heißem Wasser gespült, kochend geseift, abermals mit Wasser gespült und schließlich fertiggestellt. Es resultiert auf der Ware eine tiefe Bordo-Färbung.After the impregnation process, the web thus treated now passes through a chassis with an aqueous development liquor of 80 ° C., which

contains. The dyed textile material is then subjected to a short passage of air, then rinsed first with hot water, soaped at the boil, rinsed again with water and finally finished. A deep Bordo coloration results on the goods.

Example 3

• Lösung 1): in 180 1 Wasser von 60°C 800 g Oleylmethyltaurin und danach 30,6 kg der Diazoaminoverbindung aus diazotierter Azoic Diazo Component 2 mit der C.I.-Nr. 37 005 und Cyanamid.
• Lösung 2): 9 kg von Azoic Coupling Component 29 mit der C.I.-Nr. 37 530 mit Hilfe einer Mischung aus 9 1 Ethanol denat., 4,5 1 Natronlauge (32,5 %ig) und 18 1 Wasser von 40°C, ohne den sonst üblichen Formaldehydzusatz.
• Badansatz): Mit Wasser von 20°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 Ethanol denat. hinzu.

For dyeing 400 kg of a cotton cord fabric, 300 liters of an aqueous liquor are made up. To do this, solve

• Solution 1): in 180 l of water at 60 ° C, 800 g of oleyl methyl taurine and then 30.6 kg of the diazoamino compound from diazotized Azoic Diazo Component 2 with the CI no. 37 005 and cyanamide.
• Solution 2): 9 kg of Azoic Coupling Component 29 with the CI no. 37 530 with the help of a mixture of 9 liters of ethanol denat., 4.5 liters of sodium hydroxide solution (32.5%) and 18 liters of water at 40 ° C., without the usual addition of formaldehyde.
• Bath batch): With water at 20 ° C., solution 1) is first made up to 250 1 liquor and 600 g of a sequestering agent based on sodium ethylenediamine-tetraacetic acid, 3 1 sodium hydroxide solution (32.5%) and 10 1 ethanol are added denat. added.

Then solution 2) is stirred into the bath batch and this is filled up with water at 20 ° C. to a total volume of 300 l.

With the liquor prepared in this way, the cord fabric is impregnated by direct transfer without dipping it at 25 ° C. and with 35% liquor absorption with the aid of a device for minimal dosing as in Example 1. Immediately afterwards, the goods treated in this way are exposed to a short airflow at room temperature.

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

zuerst bei 70°C und dann kochend geseift, anschließend erneut mit Wasser gespült und fertiggestellt.For this purpose, the impregnated cord is treated on the foulard with 100% liquor absorption, the textile material is then subjected to an air passage of 30 seconds at room temperature and the dyeing obtained in this way is rinsed in a wide washing machine with water at 70 ° C. in the first box. In the remaining boxes of the wide-width washing machine, the dyed goods are placed in an aqueous bath under the effect of

first at 70 ° C and then soaped at the boil, then rinsed again with water and finished.

You get a bright orange color.

Example 4

A fabric made of regenerated cellulose fibers is impregnated with an aqueous liquor at room temperature and the following composition by direct transfer without dipping it using a minimal application device as in Example 1 with a liquor application of 40%:

The fabric impregnated in this way is now steamed for 5 minutes at 185 ° C. in the superheated steam for dye development. The dyed textile material is then rinsed with water and aftertreated for 10 minutes at 90 ° C. with an aqueous bath with the addition of 1 g / l of an approximately 20-fold ethoxylated nonylphenol.

A brilliant red color with good fastness properties is obtained.

Example 5

• Man löst zu diesem Zweck
  • a) 8,8 kg von Azoic Coupling Component 12 mit der C.I.-Nr. 37 550 mit Hilfe einer Mischung aus 27,5 1 Ethanol denat., 3 1 Natronlauge (32,5 %ig) und 10 1 Wasser von 60°C;
  • b) in 200 1 Wasser von 20°C 800 g Oleylmethyltaurin und danach 24 kg der Diazoaminoverbindung aus diazotierter Acoic Diazo Component 5 mit der C.I.-Nr. 37 125 und Cyanamid
• und versetzt die Lösung mit einem Gemisch aus
  

540 kg of a terry toweling fabric are to be dyed. For this purpose, the textile material is treated with 440 l of an aqueous liquor using a minimal application device as in Example 1 by direct transfer without immersion thereof, which are obtained in the manner indicated below:

• One solves for this purpose
  • a) 8.8 kg of Azoic Coupling Component 12 with the CI no. 37 550 with the help of a mixture of 27.5 1 ethanol denat., 3 1 sodium hydroxide solution (32.5%) and 10 1 water at 60 ° C;
  • b) 800 g of oleylmethyl taurine in 200 l of water at 20 ° C. and then 24 kg of the diazoamino compound from diazotized Acoic Diazo Component 5 with the CI no. 37 125 and cyanamide
• and adds a mixture to the solution
  

Then you stir solution a) in solution b) and fill the bath with water at 20 ° C to the total volume of 440 1.

After the textile goods have been impregnated twice at 20 ° C and with a total liquor absorption of 70%, they are steamed for 3 minutes at 102 ° C while wet.

aufweist, bei 80°C und 20 Sekunden Tauchdauer der Azofarbstoff auf der Faser entwickelt. Danach wird diese 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/1 Oleylmethyltaurin im wäßrigem Bad geseift. In den Kästen 7 und 8 wird die gefärbte Ware schließlich warm (60°C) und kalt mit Wasser gespült und abgespritzt. Danach wird das Verfahrenserzeugnis getrocknet.Immediately after steaming is now carried out in a continuous manner by treating the impregnated goods in the first box of a wide-angle washing machine with an aqueous bath which

has developed at 80 ° C and 20 seconds immersion of the azo dye on the fiber. Then this dyeing is 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 while boiling with 1 g / 1 oleylmethyl taurine in an aqueous bath. In boxes 7 and 8, the dyed goods are finally rinsed with water warm (60 ° C) and cold and sprayed. The process product is then dried.

You get a full, bright wine red color with a soft, full handle of the terry goods.

In the above example, the double minimum application of the impregnation liquor can be carried out from the different sides of the textile web in order to achieve a more uniform distribution of the treatment agent on the terry goods and their better penetration.

Claims (2)

1. A process for the dyeing of textile fabrics or web-like textile articles made of cellulose fibers or their blends with synthetic fibers, with coupling component and diazo component in the form of a stabilized diazoamino or tetrazoamino compound or a diazotate on the fiber produced by the dye-forming components continuously and together by direct transfer from an aqueous liquor containing these substances under alkaline conditions to the goods without dipping the textile goods therein and the subsequent dye development is brought about by the action of acid, characterized in that the impregnation process of the two dye-forming components containing one another is carried out Float at the intended location on the substrate surface by means of the even application of small amounts of liquid (minimum order rag) effecting application measure and then proceeding to release the coupling-capable diazonium compound and coupling in a conventional manner. 2. The method according to claim 1, characterized in that in the course of the minimum order fleet intake quantities through the textile goods in the range between 15% and 50% (based on the weight of the dry goods).