EP0058433B1 - Process for the continuous dyeing and printing of wool fibres - Google Patents

Description

The present invention relates to the continuous dyeing and printing of wool fibers with reactive dyes containing sulfo groups in the presence of alkali acetate and without the use of textile auxiliaries after a block quick steaming process or a pressure quick steaming process.

The continuous dyeing of wool fibers, especially in the form of sliver, threads, bundles of yarn, but also fabrics, with reactive dyes without the use of textile auxiliaries or without being forced to work with two-phase dyeing liquors, can not yet be used for carry out the necessary safety and reproducibility of the nuance. On the one hand, it is the steaming times that take too long for an economical, energy-conscious dye fixation; on the other hand, in the previously known dyeing processes, this always results in high amounts of waste water contaminated with surface-active products, the treatment of which is rather cumbersome and also costly.

For example, it is known from PE-C-2244524 to process wool comb with the help of Vigoureux printing into uniformly colored melanges, the authenticity properties of the color effects which can be achieved in this way being superior to those of other dye classes primarily because of the reactive dyes used. The steaming times for dye fixation - exposure times at 100-102 ° C of 15 to 40 minutes are recommended for Vigoureux printing - can be described as short for the technical development at that time, just as a preliminary drying does not seem necessary. However, in the known process for full fixation of the reactive dyes, urea as a solubilizer and at the same time as a fixing aid must also be added to the printing pastes; an acetic acid / sodium acetate buffer serves to adjust the pH.

Furthermore, in the sample card Hoe 2990 «®REMAZOL dyes for printing by Hoechst AG, Frankfurt / Main, a fabric printing process for wool is explained, in which reactive dyes of the vinyl sulfone type are printed together with sodium acetate and urea on woolen fabric, dried and fixed be steamed in saturated steam. The last-mentioned recipe prescribes urea quantities of 150 to 200 g / kg of printing paste and, in this case, intermediate drying, the steaming time is 10 to 15 minutes.

In contrast to this, in the wool application area, continuous dyeing of yarn by dye impregnation and fast-acting fixation, similar to that of printing processes, has so far not been achieved with comb pulling, thread coulters and yarn bundles. Only when printing on webs - due to the relatively small covered areas, which are surrounded by unprinted and therefore dry areas - was it possible to allow a steaming time in the range of 10 to 15 minutes as the shortest fixing time. In this way, the heating of the printed surfaces is much faster than if you have to heat a textile material that is continuously moist throughout its entire width. On the other hand, other prerequisites exist if all such continuous dyeing and printing processes of wool fibers are included in such an investigation, which are either aimed at the use of specific dyes which balance out the affinity differences within the wool fiber, such as, for. B. Methyltaurino-ethyl sulfone reactive dyes according to DE-C-23 40 044, where from a neutral or only slightly different medium and without intermediate drying is carried out by a steam fixing method and the impregnating liquors to prevent the gray haze on the dyeings produced a mixture of anionic and non-ionic surfactants must be added; or the above-mentioned check also extends to continuous dyeing techniques which are carried out under the influence or in the presence of textile auxiliaries or substances having a similar effect. This subheading also includes products that allow working in two-phase dyeing liquors. Processes in the previously discussed category entail high water consumption and therefore require a lot of energy and a correspondingly large amount of labor. Today, however, energy savings and easy-to-remove wastewater play an important role.

The invention explained below is based on the object of eliminating the disadvantages known from the prior art and of realizing a very fast-running process for the continuous dyeing and printing of wool fibers with sulfo-containing reactive dyes, which particularly greatly reduces the steaming time. As already mentioned at the beginning, fixing times of at least 10 minutes for fixing dyes on animal fibers are the minimum that has been available up to now. However, shorter realizable processes and faster dyeing techniques would offer the possibility of better energy utilization and also allow higher production speeds. In addition, the mandatory use of textile auxiliaries should be as low as possible, so that the emission of such polluted wastewater is largely reduced.

This object is achieved according to the invention in that the fiber material to be dyed or printed is mixed with an aqueous dye liquor containing 60 to 100 g, preferably 80 to 90 g of sodium acetate per 1 in addition to the dissolved dyes, or an aqueous solution containing this amount of sodium acetate per kg Printing paste blocks or prints, the block or the print briefly between drying and then for dye fixation 30 to 180 seconds, preferably 60 to 120 Subjected to saturated steam at temperatures from 102 ° to 115 ° C for seconds. The drying is expediently carried out below 100 ° C.

The feasibility of the new process is based on the principle of adding very large amounts of sodium acetate to the padding liquor or printing paste combined with a subsequent rapid steaming process after the padding or printing has previously been dried with the reactive dyes. Under this condition, the method of operation according to the invention allows the wool material to be continuously dyed or printed without the involvement of additional textile auxiliaries or solubilizers. It is irrelevant whether the wool material is subjected to Vigoureux, film or Rouleaux printing.

The claimed method is first and foremost a very quickly applicable dyeing or printing technique, which does not require any special machine park tailored to it and which is distinguished, above all, by the fact that a high color yield is achieved. The level of authenticity that can be achieved with the high color strength of the process products must be regarded as surprising. The extraordinarily good fastness properties result from the covalent bond between dye and wool fiber that takes place within a very short time, which in turn has its origin in the use of sodium acetate. In order to achieve the high level of authenticity described, no additional measures such as pH control etc. need to be taken, so that the implementation of the method described is very simplified.

In relation to the present invention, it was astonishing and even a person skilled in the art had not expected that, depending on the color depth, 60 to 100 g of sodium acetate per liter of padding liquor or per kg of printing paste would result in the reaction course of the fixing operation, which is known per se, according to the scheme is accelerated, so that continuous process control can be made possible in this case. However, this also means that - because large amounts of sodium acetate are available - these then make a direct contribution to the fixation of the dyes used and, consequently, the steaming times required for this can be kept low.

Likewise, it was not easy to predict that the colors would be extremely unimportant under these conditions. In Textile Practice 1971, pages 164-167, in particular 167, it is emphasized that the levelness of dyeing wool with reactive dyes becomes better as the pH decreases, and does so significantly better. It is simply not at all obvious that the sodium acetate, which reacts in a clearly alkaline manner in these quantities, can be obtained at all.

It is regarded in professional circles as a rule of thumb that experience generally requires high temperatures for fixing dyes in fiber materials with a short exposure time, whereas when temperatures are applied - in a temperature range that is only slightly above 100 ° C - the Heat exposure time must last correspondingly longer for the intended process. An arbitrary use of this observation in the direction of a reduction in the fixing time is, however, limited in the present case by the fact that pure, unmixed wool fiber materials can only be subjected to such a heat treatment for the aforementioned purpose at temperatures of 100 ° to 115 ° C., because above At 115 ° C the wool is damaged by the influence of the heat. However, as has been determined according to the invention, the use of sodium acetate in turn enables a further reduction in the exposure time without the steam temperature of 115 ° C. needing to be exceeded. As a result, the duration of the heat exposure can be shortened very greatly with very high amounts of sodium acetate. The increase in the amount of sodium acetate in the course of the invention therefore brings with it an enormous saving in time for fixing the dye on wool. The color depths in the claimed process are surprisingly good despite the remarkably short fixing times for animal fibers, and the fastness properties correspond to the standard.

On the other hand, fiber damage does not occur in the course of the dyeing process according to the invention in view of the use of the unusually high amounts of sodium acetate, although at the beginning of the treatment the pH value of the padding liquor and also of the printing paste is about 9. Firstly, the exposure time in this environment is very short, it is only a few seconds, and immediately after the goods enter the steamer, acetic acid is released, which then shifts the pH value to weakly acidic. Towards the end of the steam treatment, however, the fixing medium is shifted back to alkaline, but this state also lasts only seconds and at the same time replaces an alkaline aftertreatment of the dyeings or prints produced.

The specific nature of the dyeing conditions makes it possible to dispense with the leveling agents that are usually used for dyeing wool. You still get very uniform colors. However, leveling agents or retardants should not be added easily when the new process is carried out; if necessary, they can prove to be disruptive. If necessary, of course, certain circumstances, for example adding an urea may appear advantageous as long as it is within the limits where there is no fear of damage to the wool. However, this is not of crucial importance for the practicability of the new method in practice. However, such an addition does not do any harm and in no way has a negative effect on the technological and also the fastness properties of the wool dyeings produced in this way. Tear resistance tests have confirmed this. Previous continuous or semi-continuous dyeing processes, on the other hand, have prescribed the use of 80 g / l of urea as the minimum minimum amount; the maximum amount in this regard is up to 300 g / l. Clearly longer steaming times are required in all such known methods.

A very special advantage is the stability of the padding liquors and printing pastes under the given conditions, which is over 24 hours in this very weakly alkaline environment. This makes the entire dyeing process easier to handle.

As fiber material for the claimed process, wool fibers are particularly suitable in the form of a sliver of yarn, thread coulters and bundles of yarn, but also fabrics. Of course, individual threads can also be treated in this way, but the effectiveness of the method is questioned in this case. The new process is also suitable for dyeing or printing the wool content of fiber blends.

The process according to the invention can be particularly important for the patterning of carpets made of pure wool. With the short fixing times which characterize this working method, not only a high material production but also a simple process sequence can be achieved. In the simplest case, the substrate is carpeted or patterned according to the type of TAK dyeing process. In this way, a large number of individual pieces can be produced, which are characterized by an individual pattern.

The dyeing or printing technique according to the present invention can also be applied to wool fibers which have been subjected to a “felt-free” finishing process - such wool is generally referred to as “superwashed” wool. These are wool fibers which, for. B. with a polyimine or polyacrylic resin film (according to the information in Melliand Textile Reports 9/1971, page 1100, or in the Journal of the Society of Dyers and Colors, Volume 88, Number 3/1972, pages 93-100) are. A textile article made from it must be able to withstand the hard stresses not required and not achieved with normal wool, such as washing multiple times at 60 ° C with the use of household detergents containing perborate, without matting, and consequently be color-fast. Such requirements at this high level of fastness, particularly in terms of fastness to washing and sweating, are primarily achieved by dyeing and printing with reactive dyes.

In the case of wool finished in this way without felting, the results obtained in the dyeing or printing according to the invention are as good as in the case of normal wool. This fact is surprising in that the felt-free finished wool has a different drawing power than the untreated wool fibers show. Nevertheless, this different behavior does not require special consideration when creating a coloring or printing recipe. This makes the new process the only one of its kind to date, in which the same depth of color and the same levelness can be achieved on both finished and non-finished wool fibers according to one and the same rule.

For dyeing or printing the wool fibers or the wool portion of fiber mixtures according to the present process, the organic dyes known under this term - regardless of the type of their reactive group - are suitable as reactive dyes. This class of dyes is referred to in the Color Index, 3rd edition 1971 as “reactive dyes”. These are predominantly those dyes which contain at least one group which is reactive with the amino groups of polyamide fibers, a precursor therefor or a substituent which is reactive with the amino groups of polyamide fibers. Particularly suitable as the basic body of the organic dyes are those from the series of the azo, anthraquinone and phthalocyanine dyes, it being possible for the azo and phthalocyanine dyes to be both metal-free and metal-containing. Reactive groups and precursors which form such reactive groups include, for example, epoxy groups, the ethyleneimide group, the vinyl grouping in the vinylsulfone or acrylic acid radical, also the β-sulfatoethylsulfone group, the β-chloroethylsulfone group or the β-dialkylaminoethylsulfone group. In addition, derivatives of the tetrafluorocyclobutyl series, e.g. B. the tetrafluorocyclobutyl acrylic acid in question. The reactive substituents in reactive dyes are those that are easily removable and leave an electrophilic residue. Examples of suitable substituents are 1 to 3 halogen atoms on the following ring systems: quinoxaline, triazine, pyrimidine, phthalazine, pyridazine and pyridazone. Dyes with several identical or different types of reactive groups can also be used. Such reactive dyes of the type defined above often have more than one sulfonic acid group (apart from the reactive constituent of the dye) in the molecule, which can be distributed as desired over the chromophore, but are preferably bound to its aromatic radicals. Based on the color yields achievable with conventional exhaust processes, the dyes mentioned above give very good yields on wool in the case of the continuous process according to the invention.

DE-A-20 57 400 also relates to a continuous process according to which the block dyeing and printing of textile material made of non-chlorinated wool with reactive dyes together with dye fixation - expediently after preliminary intermediate drying - is described by steaming with saturated steam. Although it is clear from the recipe of the exemplary embodiments there that, in addition to a not insignificant addition of urea, the padding liquors or printing pastes used in accordance with this prior art also contain sodium acetate in a lower concentration than in the process according to the invention, the difference is based on the present one Invention this known dyeing technique in particular on the mandatory use of Aids with a surface-active effect, e.g. B. fatty acid polyglycol esters, in amounts of 2 to 10 wt .-%. The presence of the last-mentioned substances is primarily aimed at making the pretreatment of the fiber material by chlorine, which is otherwise necessary to achieve full and deep shades with good brilliance, unnecessary. However, the inevitable involvement of tools of the type mentioned above is avoided by the method of operation according to the invention.

example 1

• 20 g des Farbstoffes Reactive Blue 19 mit der C.l.-Nr. 61200,
• 70 g Natriumacetat und
• 10 g m-nitrobenzolsulfonsaures Natrium.

Wool yarn from non-chlorinated wool is padded in the form of parallel yarn bundles at room temperature and a liquor absorption of 110% (by weight of the dry goods) by dipping and squeezing three times with an aqueous liquor which contains 1 liter

• 20 g of the dye Reactive Blue 19 with the Cl no. 61200,
• 70 g sodium acetate and
• 10 g sodium m-nitrobenzenesulfonic acid.

The fiber material is then dried at 90 ° C and then immediately passed through a steamer and steamed there for 3 minutes in saturated steam at 110 ° C.

• 1 g/I eines nichtionischen Waschmittels enthaltend 30 Gew.-% eines Umsetzungsproduktes von 1 Mol Stearylamin mit 12 Mol Ethylenoxid, und
• 1,5 ml/I Ammoniak (pH 8,5)

5 Minuten lang bei 55 °C geseift. Zuletzt wird die gefärbte Ware nochmals warm und kalt mit Wasser gespült. Man erhält auf dem Garn eine dunkelblaue Färbung.The textile material treated in this way is then rinsed first with cold water, then with water at 40 ° C. and finally in an aqueous bath with the addition of

• 1 g / l of a nonionic detergent containing 30% by weight of a reaction product of 1 mol of stearylamine with 12 mol of ethylene oxide, and
• 1.5 ml / l ammonia (pH 8.5)

Soaped at 55 ° C for 5 minutes. Finally, the dyed goods are rinsed warm and cold with water. A dark blue color is obtained on the yarn.

Example 2

• 16 g des Reaktivfarbstoffs der Formel
  
• 80 g Natriumacetat und
• 10 g m-nitrobenzolsulfonsaures Natrium enthält.

Chlorinated wool fabric (plain weave) is padded at 25 ° C and a liquor absorption of 100% (by weight of the dry goods) with an aqueous liquor, which is in liters

• 16 g of the reactive dye of the formula
  
• 80 g sodium acetate and
• Contains 10 g of sodium m-nitrobenzenesulfonate.

The wool material is now dried at 85-90 ° C. and then steamed at 113 ° C. for 120 seconds in a steamer and then aftertreated as described in Example 1. A strong red color is obtained.

Example 3

• 16 g des Reaktivfarbstoffs der Formel
  
• 90 g Natriumacetat und
• 10 g m-nitrobenzolsulfonsaures Natrium enthält.

Knitted fabric made of chlorinated wool fibers is padded with an aqueous liquor, which is in liters, at room temperature and a liquor intake of 95% (by weight of the dry fabric)

• 16 g of the reactive dye of the formula
  
• 90 g sodium acetate and
• Contains 10 g of sodium m-nitrobenzenesulfonate.

The fiber material is now dried at about 90 ° C and then steamed at 115 ° C for 60 seconds. The dyed goods are aftertreated as described in Example 1. A clear, strong orange shade is obtained.

Example 4

• 15 g des Farbstoffs Reactive Red 4 mit der C.l.-Nr 18 105,
• 95 g Natriumacetat und
• 80 g Harnstoff enthält.

The wool comb, which has been equipped with a polymer-free polyamide-epichlorohydrin, is padded with an aqueous liquor at room temperature and a liquor absorption of 110% (by weight of the dry goods), which is in liters

• 15 g of the dye Reactive Red 4 with the Cl No. 18 105,
• 95 g sodium acetate and
• Contains 80 g of urea.

In addition, 10 g of sodium m-nitrobenzenesulfonic acid are added to the padding liquor as a reducing protection agent.

• 1 g/I eines nichtionischen Waschmittels enthaltend 30 Gew.-% eines Umsetzungsproduktes von 1 Mol Stearylamin mit 12 Mol Ethylenoxid, und
• 1,5 ml/I Ammoniak (pH 8,5)

5 Minuten lang bei 55 °C geseift. Anschließend wird die gefärbte Ware warm und kalt mit Wasser gespült. Man erhält eine sehr kräftige Rotfärbung auf dem Wollkammzug.The fiber material is now dried at about 85 ° C and then passed through a steamer, where it is steamed at 115 ° C for 50 seconds to fix the dye. The textile material treated in this way is then rinsed first with cold water, then with water at 40 ° C. and then in an aqueous bath with the addition of

• 1 g / l of a nonionic detergent containing 30% by weight of a reaction product of 1 mol of stearylamine with 12 mol of ethylene oxide, and
• 1.5 ml / l ammonia (pH 8.5)

Soaped at 55 ° C for 5 minutes. The dyed goods are then rinsed warm and cold with water. You get a very strong red color on the wool ridge.

Example 5

• 20 g des Reaktivfarbstoffs der Formel
  
• 700 g Alginatverdickung
• 100 g Harnstoff
• 90 g Natriumacetat und
• 10 g m-nitrobenzolsulfonsaures Natrium

sowie als Ausgleich Wasser, bedruckt, wobei man eine Rotationsfilmdruckmaschine einsetzt oder den Druck auf Filmdrucktischen durchführt.Fabric made from chlorinated wool fibers is made with a printing paste consisting of 1 kg

• 20 g of the reactive dye of the formula
  
• 700 g alginate thickening
• 100 g urea
• 90 g sodium acetate and
• 10 g sodium m-nitrobenzenesulfonic acid

as well as water to compensate, using a rotary film printing machine or printing on film printing tables.

The printed fiber material is now dried at 90 ° C and immediately steamed at 114 ° C for 60 seconds. The aftertreatment of the goods is carried out as shown in Example 4. You get a strong yellow print on the wool material.

Example 6

• 20 g des Farbstoffs der Formel
  
• 680 g Alginatverdickung,
• 80 g Harnstoff,
• 80 g Natriumacetat und
• 10 g m-nitrobenzolsulfonsaures Natrium sowie als Ausgleich Wasser enthält.

The wool comb is printed using the Vigoureux printing process with a printing paste per kg

• 20 g of the dye of the formula
  
• 680 g alginate thickening,
• 80 g urea,
• 80 g sodium acetate and
• Contains 10 g of sodium m-nitrobenzenesulfonate and water as compensation.

After intermediate drying at 85 ° C., the printed goods are steamed at 112 ° C. for 150 seconds and then post-treated as described in Example 4. The result is a deep, bright blue on the wool comb that can be processed into corresponding melanges.

Claims (8)

1. A process for the continuous dyeing and printing of wool fibers with reactive dyes containing sulfo groups, in the presence of an alkali metal acetate and without the application of a textile auxiliary agent according to a pad-rapid steaming method or a print-rapid steaming method, characterized in that the wool fiber material to be dyed or printed is padded with an aqueous dyebath containing sodium acetate in the range of from 60 to 100 g per liter of liquor in addition to the dissolved dyestuffs, or is printed with an aqueous print paste containing sodium acetate in the foregoing mentioned amount per kilogram of paste, and after a short intermediate drying, said pad dyeing or print is subjected to a treatment with saturated steam at a temperature in the range of from 102 to 115°C for 30 to 180 seconds, to fix the dyestuffs.

2. A process according to claim 1, characterized in that the amount of sodium acetate is in the range of from 80 to 90 g per liter of the padding liquor or per kilogram of the print paste.

3. A process according to claim 1 or 2, characterized in that the padding liquor or the print paste further contains urea in addition to the dissolved dyestuff.

4. A process according to one or several of the claims 1 to 3, characterized in that the padding liquor or print paste additionally contains sodium m-nitrobenzene sulfonate.

5. A process according to one or several of the claims 1 to 4, characterized in that the time of treatment with steam is 60 to 120 seconds.

6. A process according to one or several of the claims 1 to 5, characterized in that an intermediate drying is applied to the wool fibers after removing excess of the dyeliquor.

7. A process according to one or several of the claims 1 to 6, characterized in that wool fibers in form of slubbing, yarn, warp and yarn bundles are dyed or printed.

8. A process according to one or several of the claims 1 to 7, characterized in that wool fibers having an antifelting finish in the form of a coating layer of a polyimine resin or a polyacrylic resin are dyed or printed.