DE3105906A1 - METHOD FOR CONTINUOUSLY DYING WOOL FIBERS - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 81 / F Ο36 Dr.CZ/cr Process for the continuous dyeing of wool fibers

The present invention relates to the continuous and even 'fast dyeing of wool fibers with sulfo groups Reactive dyes using a pad-steaming process without intermediate drying.

The continuous dyeing of wool fibers, especially in the form of tops, bundles of threads, bundles of yarn, but also Woven fabrics with reactive dyes without the use of textile auxiliaries or without being forced to use Having to work two-phase dye liquors has not yet been achieved with the one required in practice Perform security and reproducibility of the nuance. On the one hand, it is the steaming times which take too long for economical, energy-conscious dye fixation; on the other hand fall with the previously known Dyeing processes on this basis always high amounts of contaminated with surface-active products Wastewater, the treatment of which is rather cumbersome and also expensive.

For example, from DE-PS 22 44 524 it is known to process wool comb with the help of Vigoureux printing into uniformly colored melanges, the fastness properties of the color effects that can be achieved in this way being superior to those of other dye classes primarily due to the reactive dyes used. The Dämpfseiten for dye fixation - it is recommended when Vigoureuxdruck exposure times at 100-102 ⁰ C. of 15 to 40 minutes - can be well described as short for those technical development. However, you have to

known method for a full fixation of the reactive dyes the DruckDasten nor urea

as a solubilizer and at the same time as a fixation aid Add an acetic acid / sodium acetate buffer is used to adjust the pH value.

Furthermore, in the sample card Hoe 2990 "®REMAZOL dyes für die Druck "of Hoechst AG, Frankfurt / Main explains a fabric printing process for wool, in which Vinyl sulfone type reactive dyes printed on woolen fabrics together with sodium acetate and urea, Intermediate drying and steaming in saturated steam for fixation. The last mentioned recipe writes urea quantities of 150 to 200 g / kg for the purpose of deepening the color Print pass before.

In contrast to this, wool in the field of application is a continuous dyeing of yarn by dye impregnation and fast-acting fixation has so far only been realized in the treatment of a single thread but not in the case of tops, sheets and bundles of yarn. Unless one refers to such a Investigation of all continuous dyeing processes of full fibers, which either rely on the use of Pacific, The affinity differences within the wool fiber are aligned to compensate for the affinity differences, such as methyltaurino-ethylsulfone reactive dyes according to DE-PS 23 40 044, where from neutral or only slightly deviating medium and without intermediate drying after a steam fixing method is used and the impregnation liquors to prevent the gray haze A mixture of anionic and nonionic surfactants must be added to the dyeings produced; or one the aforementioned review also extends to continuous dyeing techniques, which are under the influence or in the presence be carried out by textile auxiliaries or substances with a similar effect. Also belong here those products that allow working in two-phase dye liquors. Processes of the category discussed above

involve high water consumption and consequently require the consumption of a lot of energy as well correspondingly large effort in manpower. Nowadays, however, energy savings and simply play a role wastewater disposal plays an important role.

The invention explained below is now based on the object of addressing the disadvantages outlined at the beginning the known processes for the continuous dyeing of wool fibers with reactive dyes containing sulfo groups to fix in relation to the length of the dyeing time and especially to achieve a shortening of the steaming time. In addition, the mandatory use of Texcil auxiliaries should be as low as possible, so that the output is largely reduced in such polluted wastewater.

According to the invention, this object is achieved in that the fiber material to be dyed with a further 20 to 50 g / l, preferably 30 to 40 g / l, in addition to the dissolved dyes Sodium acetate, containing aqueous dye liquor, and after removing the excess liquor, the wet Padding for the purpose of fixing the dye for 5 to 13 minutes, preferably 9 to 12 minutes of the action of Subjects saturated steam at temperatures from 102 ° to 115 ° C.

The feasibility of the new process is based on the principle of adding large amounts of sodium acetate combined with a subsequent short-term steaming process without prior intermediate drying the padding with the reactive dyes. Here, the concentration of sodium acetate is such that it is in of the dye preparation is present in a significant excess based on the amount required for the adjustment as well as maintaining weakly acidic to neutral pH conditions would be required. Under this The prerequisite allows the method of operation according to the invention,

the woolen material without the involvement of additional textile auxiliaries or solution mediator to color continuously.

The claimed block dyeing technique is emerging mainly because a very high color strength of the process products is achieved. That way The available product image is excellent, the result is up to 100% greater color yields than the previous ones usual methods for continuous wool dyeing.

The level of fastness achievable with the high color strength of the dyeings must be regarded as surprising. The extraordinarily good fastness properties come from the fact that it takes place within a very short time covalent bond between dye and wool fiber conditions, which in turn originate in the application of Has sodium acetate. In order to achieve the high level of authenticity described, no additional ones are required Measures such as pH control etc. can be taken so that the procedure described can be carried out is very 'simplified.

In relation to the present invention it was astonishing and was not expected even by a person skilled in the art that when using 20 to 50 g / l of sodium acetate, depending on the depth of color, the known according to the scheme Reaction course of the fixing operation is accelerated so that in this case a continuous Allow process management. But this also means that - because large amounts of the sodium acetate are available stand - they then make a direct contribution to the fixation of the dyes used and you consequently can keep the steaming times required for this low.

Likewise, it was not easy to foresee that the colorations would be extraordinary under these conditions become irrelevant. In Textil-Praxis 1971, pages 164-167,

in particular, it is emphasized that the levelness of dyeing wool with reactive dyes with decreasing pH-value better, and clearly better. That in spite of this clearly with the one in these quantities alkaline-reacting sodium acetate to obtain level dyeing at all is simply by no means obvious been.

Fiber damage occurs within the scope of the invention Dyeing process does not occur, although the pH value of the padding liquor is around 9 at the beginning of the treatment. First, the exposure time in this environment is very short, it is only a few seconds, and the same then when the goods enter the steamer, acetic acid is released, which then changes the pH to slightly acidic shifts. Towards the end of the steam treatment, however, the liquor medium is shifted back to the alkaline state, but this condition also lasts only seconds and at the same time replaces an alkaline aftertreatment of the colorations produced.

The specific nature of the dyeing conditions allows them to be mostly used when dyeing wool To dispense with leveling agents. Despite this, very even colorations are obtained. Of course, certain Circumstances the presence of small amounts of such auxiliaries in the padding liquor appear advantageous permit. However, these are not decisive for the feasibility of the new method in practice Meaning. Such an addition does not do any harm and influences the authenticity properties of the in In no case did wool dyeings in this way produce a negative effect admission, as long as this is within the limits where damage is not to be feared, in none Way disturbing. In contrast, previous continuous or semi-continuous dyeing processes have been used

of 80 g / l urea prescribed as the absolute minimum amount; the maximum is in this regard at up to 300 g / l. With all such known methods, of course, significantly longer steaming times are required.

In addition, a very special advantage under the given conditions is the stability of the padding liquor, which is over 24 hours in this very weakly alkaline medium. Thus, the whole dyeing process can be handled more easily. '

However, the padding liquors used according to the invention can additionally contain thickeners so that they j

due to the more viscous hereby set [consistency according to a modification of the present

Let the invention also be used for vigoureux printing.

The rest of the process, in particular the measures *.

for dye fixation, remains the same. j

Come as fiber material for the claimed process;

Wool fibers especially in the form of tops, yarn, thread sheets i

and yarn bundles, but also fabrics. Self- j Individual threads can of course also be treated in this way, the effectiveness of the process is in in this case, however, called into question. The new process is also suitable for dyeing the wcll portion of Fiber blends.

The dyeing technique according to the present invention can also be used on wool fibers which have been subjected to a "felt-free" finishing process - such wool is generally referred to as "superwash" finished wool - \

use. These are wool fibers that j

e.g. with a polyimine or polyacrylic resin film (corresponding to the information in Melliand Textilberichte 9/1971, page 1100, or in the Journal of the Society of Dyers and

Colourists, Volume 88, Number 3/1972, Pages 93-100). A deraus manufactured textile articles must withstand not required under normal wool and also did not reach, tough conditions of a multiple wash at 60 ⁰ C with concomitant use of perborate household detergents without matted, and consequently be correspondingly colorfast. Such requirements on this high level of fastness, especially wash and perspiration fastness, are primarily met by dyeings with reactive dyes.

With such a felt-free finished wool are equally good in the context of the dyeing according to the invention Results achieved as with normal wool. This fact is surprising insofar as the felt-free finish Wool has a different pulling power than it does show untreated wool fibers. Nevertheless, this different behavior does not require any special consideration when creating a dye recipe. This makes the new process the only one of its kind so far in which according to one and the same rule on both finished and non-finished wool fibers the same Color depths and the same equality can be achieved.

For dyeing the wool fibers or the wool content of fiber blends according to the present process come as reactive dyes, the organic dyes known under this term - regardless of their nature reactive group - into consideration. This class of dye will in the Color Index, 3rd edition 1971 as "Reactive Dyes" designated. These are predominantly those dyes that contain at least one with the amino groups of polyamide fibers reactive group, a precursor for this purpose or contain a substituent which is reactive with the amino groups of polyamide fibers. As a basic body Of the organic dyes, particularly those from the series of the azo, anthraquinone and

Phthalocyanine dyes, the azo and phthalocyanine dyes can be both metal-free and metal-containing. As reactive groups and precursors that such reactive groups are, for example, epoxy groups, the ethyleneimide group, the Viny! Grouping in the vinyl sulfone or acrylic acid residue, also the ß-sulfatoethylsulfongruppe, the ß-chloroethylsulfongruppe or the ß-dialkylamino-ethylsulfone group called. In addition, derivatives of the tetrafluorocyclobutyl series, e.g. tetrafluorocyclobutyl acrylic acid, are used for this process. in question. The reactive substituents in reactive dyes are those which can easily be split off and leave an electrophilic residue. For example, 1 to 3 halogen atoms can be used as substituents at the following ringsy stars: quinoxaline, triazine, pyrimidine, phthalazine, pyridazine and pyridazone. It is also possible to use dyes with several identical or different reactive groups. 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 arbitrarily over the chromophore, preferably but are bound to its aromatic radicals. Based on dit that can be achieved with conventional exhaustion processes The abovementioned dyes provide color yields in the case of the continuous process according to the invention very good yields on wool.

The claimed method has been compared to the known dyeing methods, in which the padding liquor acetic acid, (e.g. 25-35 ml / 1 acetic acid 60%) or acetic acid together with urea instead of sodium acetate has been added, turns out to be superior. The steaming times of these previous methods are usually long longer and the resulting color strength is almost always up to 50% weaker than when working with sodium acetate will.

example 1

Woolen fabric made of non-finished wool fibers in a plain weave is padded ^{with an aqueous flute at a pad temperature of 25 0} C and a liquor pick-up of 105% (of the weight of the dry goods), which has a solution of per liter

16 g of the reactive dye of the formula

CH ₃

and contains 40 grams of sodium acetate. This padding liquor is also 10 g / 1 of sodium m-nitrobenzenesulfonate added as a reduction inhibitor.

Without intermediate drying, the still wet fibrous material will be performed immediately after the padding process through a damper, where the dye fixation for 12 minutes steamed in saturated steam at 103 ⁰ C.

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 mole of stearylamine with 12 moles Ethylene oxide, and 1.5 ml / 1 ammonia (pH 8.5)

Soaped at 55 ° C for 5 minutes. Last is the colored one Goods rinsed again warm and cold with water.

- Kf -

A very strong color in a reddish yellow is obtained.

One carried out in parallel to the above procedure Coloring in which the entire amount of the sodium acetate used there is replaced by 25 ml of acetic acid (60%) has only produced a 50% lighter (weaker) shade compared to the result there.

Dyeing same results as in the inventive example, however, is obtained if the wool material according to the present formulation padded (in the presence of sodium acetate), however, immediately followed by 10 min. At 106 ⁰ C is attenuated.

Example 2

Knitted goods made from chlorinated wool fibers are made at room temperature and with a liquor absorption of 95% (of the weight of the dry goods) padded with an aqueous liquor that per liter

16 g of the reactive dye of the formula

- CH ,, - CH "- O - SO-, Η

45 g sodium acetate and
Contains 8 g of sodium m-nitrobenzenesulfonate.

The still moist fiber material is then immediately passed through a steamer and steamed ^{there at 11 0 ° C. for 9 minutes.} The aftertreatment of the dyed goods takes place as in Example 1. A strong, brilliant orange coloration is obtained.

An analogous coloring _; however, using 150 g / l urea together with 25 ml / l acetic acid (60%) instead of 45 g / l sodium acetate results in a shade that is at least 50% lighter than the example according to the invention.

Example 3

Yarn from non-chlorinated wool is padded in the form of parallel yarn bundles at a block temperature of 30 ⁰ C and a liquor pickup of 90% (by weight of the dry goods) three times to immersion and squeezing with an aqueous liquor containing, per liter,

20 g of the dye Reactive Blue 19 with the C.I. 61200,

35 g sodium acetate and
9 g of sodium m-nitrobenzenesulfonate.

The still moist fiber material is dried without intermediate drying immediately afterwards dutch a damper and

steamed there for 7 minutes at 115 ° C. After a same Subsequent cold and warm rinsing with water is followed by an aftertreatment as described in Example 1. A navy blue dye is obtained on the yarn. 25th

If the padding liquor described above is used instead of 35 g of sodium acetate, a mixture of these is used 150 g / l urea and 25 ml / 1 acetic acid (60%) and proceed as described above for the dyeing operation, in this way dyed yarn is obtained in a bright blue, which is weaker in color compared to the example according to the invention Nuance means.

Example 4

Chlorinated woolen fabric (plain weave) is made at room temperature and with a liquor uptake of 100% (from Weight of the dry goods) padded with an aqueous liquor, which per liter

16 g of the reactive dye of the formula

SO ₀ N-I

SO ₀ -CH.

50 g sodium acetate and

Contains 10 g of sodium m-nitrobenzenesulfonate.

The still moist wool material is then steamed in a steamer for 13 minutes at 102 ^° C. without drying in between and aftertreated as described in Example 1. A strong red color is obtained.

Example 5
To carry out the dyeing, the procedure is as in Example 4, the padding liquor here containing a combination of the dyes of the following formulas and amounts:

9.1 g / l of the dye from Example 2, 5.7 g / l of the dye from Example 3, 3.4 g / l of the dye Reactive Black 5 with the

CINr. 20505 and
0.31 g / l of the reactive dye of the formula

HO ₃ SO-CH ₂ -CH ₂ -SO ₂ - / VN = NC C - COOH

HO-C

The type and amounts of the additives and how the process is carried out can also be found in Example 4. Man gets a deep, flowery black on the wool fabric.

With otherwise the same procedure, but instead of sodium acetate here using 150 g / l urea 25 ml / 1 acetic acid (60%) gives a color which is approx. 50% weaker.

Example 6

Combed wool made with polymeric polyamide-epichlorohydrin Has been made felt-free, is at room temperature and a liquor pick-up of 110% (of the weight of the dry goods) padded with an aqueous liquor that per liter

15 g of the dye Reactive Red 4 with Cl no.

18 105 and
Contains 45 g of sodium acetate.

10 g of m-nitrobenzenesulfonic acid are also added to the padding liquor Sodium added as anti-reduction agent.

Without intermediate drying, the still wet fibrous material will be immediately after the padding process durcn a damper out and there to dye fixation 11 min. At 102 ⁰ C dampened. The textile material treated in this way is then ^{rinsed first with cold water, then with warm 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 Stearylamine with 12 mol of ethylene oxide, and 1.5 ml / 1 ammonia (pH 8.5)

Soaped for 5 minutes at 55 ⁰ C. The dyed goods are then rinsed again with warm and cold water. A very strong red color is obtained.

Example 7

Combed wool is at room temperature and a liquor pick-up of 100% (of the weight of the dry goods) an aqueous liquor padded in the liter

16 g of the reactive dye of the formula

50 g sodium acetate and

Contains 10 g of sodium m-nitrobenzenesulfonate,

Without intermediate drying, the still moist wool becomes 6 minutes at 115 ° C immediately after padding muffled. The aftertreatment of the goods dyed in this way is carried out as in Example 6. The result is strong, clear Blue discoloration.

Claims (6)

- ys- HOE 81 / f PATENT CLAIMS 1. Process for continuous as well as uniform Fast dyeing of wool fibers with reactive dyestuffs containing sulfo groups according to a pad-steaming process without Intermediate drying, characterized in that the fiber material to be dyed with one next to the dissolved dyestuffs still 20 to 50 g / l sodium acetate-containing aqueous dye liquor padding and after the Remove the excess liquor from the wet pad for the purpose of fixing the dye for 5 to 13 minutes Subjects to the action of saturated steam at temperatures from 102 ° to 115 ° C. 2. The method according to claim 1, characterized in that the amount of sodium acetate in the padding liquor 30 to 40 g / l. 3. The method according to claim 1 or 2, characterized in that that the padding liquor is still m-nitrobenzenesulfonic acid Contains sodium. 4. The method according to one or more of claims 1 to 3, characterized in that the steaming time 9 to 12 minutes. 5. The method according to one or more of claims 1 to 4, characterized in that one wool fibers in Dyes the shape of the top, yarn, thread bundles and yarn bundles. 6. The method according to one or more of claims 1 to 5, characterized in that one with a Overlay made of a polyimine resin or a polyacrylic resin dyes wool with a felt-free finish.