DE2311130B1 - Process for dyeing fibers made from natural polyamides - Google Patents

Description

. 1,269,993 have been obtained, and it has proven to be very useful to refer to these in more detail in these patents explained stabilizers for active oxygen. The amount of stabilizers that can be used is within the usual framework for such substances; usually it is about 15 to 30 percent by weight of the peroxidic agent used, calculated as hydrogen peroxide. Another very beneficial one The possibility of carrying out the process according to the invention is the use of hydrogen peroxide and performic acid solutions prepared according to the indications of French patent 1565397 are composed, d. h., Among other things, certain amounts of aliphatic, aromatic or cydoaliphatic dicarboxylic acids with up to 10 carbon atoms contain.

According to the invention, the padding liquor contains hydrogen peroxide and / or performic acid in one Amount at the time of padding up to 7 percent by weight of hydrogen peroxide, based on the fibers to be colored. At what concentration of the substances mentioned this limit value is reached depends on the liquor ratio used: For the liquor ratio 1: 1, the maximum would be possible concentration of hydrogen peroxide in the liquor 70 g / l. In general amounts of 0.15 to 7 percent by weight, preferably 0.25 to 4 percent by weight of peroxidic Agent calculated as hydrogen peroxide into consideration. If you use particularly active peroxidic Agents, for example many of those in German patents 1,269,991 and 1,269,993 and especially French patent 1565397 preparations described, so you can often use smaller amounts of it without the Success of the method according to the invention would be impaired. So have become more active from these Preparations amounts in the order of about 60% of the above, i.e. H. Amounts up to about

4 percent by weight, calculated as hydrogen peroxide and based on the fibers to be dyed, has proven its worth.

In addition to the components mentioned, the padding liquor also contains those customary in such liquors Components, especially padding aids and possibly thickeners. The block aids take care of it their wetting and dispersing effect for a rapid and even penetration of the goods with the liquor and for a fine distribution of the dyes in this. As padding aids, for example, come into consideration Alkylphenol polyglycol ethers, such as octylphenol or nonylphenol hepta- or octaglycol ethers, alkylphenol polyglycol ether sulfates, such as nonylphenol diglycol ether sulfate, fatty alcohol polyglycol ether and their Sulfates, such as the adduct of 2 moles of propylene oxide and

5 moles of ethylene oxide in 1 mole of nonanol, alkylarylsulfonates, such as dodecylbenzenesulfonic acid triethanolamine, fatty acid alkanolamides, such as coconut fatty acid diethanolamide. Usually, well-balanced mixtures of such nonionic and anionic components are used as padding aids to improve their effectiveness, add derivatives of phenylglycol, such as p-chlorophenylglycol can.

The fine distribution of the dyes in the liquor can optionally be further improved by the addition of suitable solvents, such as. B. chlorinated benzene or phenol, benzyl alcohol and others. The pH of the padding liquor is adjusted as it is for dyeing from a long liquor used coloring is required.

The explanations relating to the block process apply accordingly to other impregnation methods that are used instead of padding should.

The process according to the invention leads to such a surprisingly large improvement at a low temperature the dye fixation that only thereby

ίο a sensible application of the impregnation dwell principle for coloring fibers made from natural polyamides. The procedure can be based on any fibers of this type, for example on silk and animal hair, can be used. Its greatest importance has the process of dyeing wool.

The dyed material can be in the form of fibers, threads, flakes, yarns, tops, woven fabrics, knitted fabrics or nonwovens are present.

Compared to the known processes for simultaneous dyeing and working at boiling temperature Bleaching, for example according to German Patent 1,469,609, is very much the method according to the invention rational because of the saving of chemicals and thermal energy.

Examples

In the following examples, padding liquors of the following composition were used:

0.5 g / l dye,
2.5 g / l dodecylbenzenesulfonic acid triethanolamine,

3.5 g / I addition product of 1 mole of nonanol with 2 moles of propylene oxide and 5 moles of ethylene oxide,

2 g / l octylphenol glycol ether,

2.5 g / l p-chlorophenyl glycol

pH = 5.0 (acetic acid) or 2.0 (sulfuric acid).

For the test series A to D received the padding liquors the following additions:

Series A: no addition;

Series B: 35 g / l hydrogen peroxide (calc. 100%); Series C: 35 g / l hydrogen peroxide (calc. 100%),

5.5 g / l Na ₄ P ₂ O ₇ ;

^{4: 1} Series D: 35 g / I hydrogen peroxide (calc. 100%), 7 g / I sodium tripolyphosphate,
2.5 g / l ethylenediaminetetraacetic acid

Sodium,

12.5 g / l sodium fumarate,
°° 11 g / l hydroxymethanesulfonic acid

Sodium,

5 g / l hexamethylenetetramine,
2 g / l nonylphenol decaglycol ether.
The mixture for series D corresponds to the information in French patent specification 1,565,397 (see example 7). Performic acid is produced from the mixture in the padding liquor.

Liquor pick-up 100% (= liquor ratio 1: 1), residence for 18 h at room temperature.

After padding, the piece of wool was wrapped on an axle and the dock was used for protection Surrounded with plastic film to prevent evaporation during residence (18 hours). The dock was held in slow rotation during dwell.

In order to determine how much of the applied dye was not fixed on the goods during the dwell, wool swabs of 10 g dry weight were rinsed after padding and dwell in 500 ml of distilled water at 50 ° C. for 30 minutes , being squeezed out from time to time over the surface of the water became. In the rinsing water , the amount of dye transferred into the same was then measured colorimetrically and calculated as a percentage of the amount of dye used (0.005 g). The results obtained with the various dyes are summarized in the following table; they clearly show the previously unknown beneficial effect of peroxidic agents on dye fixation at low temperatures. The values given in columns A to D mean percent by weight of unfixed dye after it has remained.

Dye 0.05% 0.5 g / l PH A. B. C. D. 1st Cl. Acid Red 151 (26900) 5.0 16.5 3.3 2.2 1.7 2. Azo dye from 4,4'-diaminostilbene
2,2'-disulfonic acid -> ■ m-cresol 5.0 7.7 0.5 0.5 0.5 3. CI. Acid Red 107 (18025) 2.0 17.2 8.1 4.2 0.5 4. CI. Acid Red 80 (68215) 2.0 33.3 20.8 2.9 1.6 5. CI Acid Violet 36 (62010) 2.0 21.7 13.5 8.7 1.9 6. CI Acid Blue 62 (62045) 5.0 38.2 11.2 8.5 8.0 7. CI Acid Red 111 (23266) 5.0 49.3 10.6 8.7 6.8 8. Dye of the formula O NH ₂ 5.0 13.5 - - 5.0 _χ I ) / SO ₃ H
; if V ι- ΐί I CH ₃ ° ^N \ A / ^CH - ^CO - ^CH - ^CH 2 / K \ ^{Br Br} SO ₃ H

Claims (1)

1 2 Fixation of the dyes and a high brilliance of the Claim: dyeing is achieved if you use the impregnation dwell principle works with a dye liquor, Method of dyeing fibers from natural- which borrowed up to 7 at the time of impregnation Polyamides in brilliant pastel shades with 5 weight percent, based on the fibers to be dyed, Dyes that absorb from an acidic medium in the case of hydrogen peroxide or the equivalent amount low temperature, which means that it contains performic acid. draws that after the impregnation the process according to the invention makes use of the Dwell principle works with a dye liquor, the impregnation dwell principle, d. i.e., the dye liquor will at the time of impregnation, up to 7 gel oats at low temperature in the fiber material to be dyed weight percent, based on the to be colored introduced, either for compliance Fibers, hydrogen peroxide or the equivalent of a short liquor ratio in the size contains equivalent amount of performic acid. Order around 1: 1, for example from 1: 0.7 to 1: 1.3, ensures or, if a larger amount of liquor is used, then converts it to a liquor intake 100%, for example reduced from 70 to 130%, and the fiber material impregnated in this way is then left to its own devices for a long time at a low temperature. That The present invention relates to an improved impregnation, e.g. B. with a padder or method for dyeing fibers from natural ao by dipping or spraying and optionally on polyamides, which follows the impregnation / dwell principle of squeezing, centrifuging or serving, blowing the excess liquor. Under “never-usually wool and other natural temperatures” is a temperature under polyamide fibers both with metal-free acid dyes ^{- 50 °} C down to 0 ^° C, preferably such materials and with metal complex dyes at as between 15 and 35 ^C to understand C; Colored in an acidic medium, generally at boiling temperature, which is most expedient, with the prevailing coloring time in most cases being 1 hour. Also light dye ambient temperature to work. At temperatures tones are usually at 100 ° C, but at least at 20 ° C 80 ⁰ C are colored for the present process, although that are relatively low on the fiber to be fixed residence times of 10 to 24 hours, preferably amounts of dye. 30 12 to 18 hours are appropriate, the cheapest time to stay. Light, brilliant shades of color can be easily determined by means of a preliminary test. In general, it is advisable to phase out the residence metal-free acid dyes and reactive dyes during the night hours when they are not working.
applies, metal complex dyes less. The process according to the invention can in principle be carried out with all the dyes which, before the dyeing of pastel shades, draw from an acidic medium onto natural polyamide fibers in order to obtain the necessary brilliance of the dyeing. It has proven to be particularly advantageous in Verreichen. Lately it has been possible to produce these shades in connection with metal-free acid dyes in a single operation by bleaching the acidic ones directly in the acidic dyebath. Especially the 40 azo dyes and the acidic anthraquinone dyes, oxidative bleaching in the dye bath is very effective. 1: 1 metal complex dyes and 1: 2 metal complex This one-step bleaching and dyeing can be carried out both plex dyes can in principle also be used in the exhaust process (long liquor) and in the process according to the invention, pad steaming process. For stabilization of the dyes that does not form complexes in the dye liquor, however, additives are added after the dyes, which deprive these dyes of their previous knowledge and can thus damage the central atom at higher temperatures. however, they come because of their low brilliance It has also been known that wool dyeings are less of a consideration than the metal-free dyes.
Reactive dyes produced at room temperature One or more dyes can be used in the dyeing industry if the wool is used before dyeing in quantities that are otherwise particularly sensitized (oxidative or reductive) and padding liquors to achieve pastel shades are usually used in an alkaline medium colors (ETFell: are. Stevenson method for continuous top draw- Essential for the success of the invention Veredlung, Melliand, 47 [1966], 64). Process is the water content of the padding liquor There has long been a desire to use dye peroxide or performic acid as well. This group of substances substances that are absorbed from an acid medium, dyeing is also referred to in the following as "peroxidic agents" labeled on natural polyamide fibers using. to achieve the lowest possible temperatures; the hydrogen peroxide can be arbitrarily konzenbisherigen attempts in this direction in the form of but have centrated solutions are added into the padding liquor, revealed that at dyeing temperatures below 50 ⁰ C 60 is preferred to use the commercially available unmangelhafte fixation of the dyes and thus endanger 30 to 50% Solutions. However, high losses of colorant can also occur and, in addition, the colorations in the form of an addition compound made from urea lose their brilliance. and hydrogen peroxide can be used. It has now surprisingly been found that formic acid can, for example, according to the information given, avoid these disadvantages and that in the 65 of German Patent 1,272,876 produced there can be dyeing of fibers made from natural polyamides. However, it is particularly advantageous to use performe iron pastel shades with acidic solutions which are absorbed from an acidic medium and which, according to the pre-dyestuffs, produce good writings in German patents 1,269,991 and