DE724494C - Process for dyeing animal fibers with acidic dyes, optionally containing chromium in complex bonds - Google Patents

Description

Process for dyeing animal fibers with acidic, optionally Dyes containing chromium in complex bonds When dyeing animal fibers it is usually necessary to start the dyeing process in order to achieve strong staining Boiling point or with the addition of relatively large amounts of organic or inorganic acids. Working at boiling temperature as well the high acid concentration of the dyebath often damages the ones to be dyed Goods as well as damage to the acid-sensitive parts of the dyeing devices as a result, and some dyes are only insufficiently absorbed in spite of these measures on the fiber.

It has now been found that the disadvantages mentioned above can be avoided and animal fibers also below the boiling point with acidic, optionally metal can dye in a complex bond containing dyes, if the dyed material from acid dyebaths with a content of water-soluble or water-dispersible Nitrogen bases with trivalent or pentavalent nitrogen, which deal with the coloring matter implement and at least one aromatic or one aliphatic radical with at least 6 carbon atoms, but. no sulfonic acid groups or polyglycol ether chains with contains more than 3 glycol residues in the molecule, or after pretreatment with solutions such nitrogen bases from the usual acidic dyebaths below the boiling point colors. The nitrogen bases can also be used in the form of their salts. That Dyeing can be done using the usual or lesser amounts of acid.

Suitable nitrogen bases of the type mentioned are, for example, amines which, in addition to the higher molecular weight radical, also contain oxyalkyl radicals, e.g. B. Laury1monoäthanolamin or Cetyldiäthanolamin (obtainable by the method of British Patent 369 61q., Example 13), also esters of Oxalkylaminen, z. B. mono-, diodes triethanolamine, dimethylethanolamine or phenylbutanolamine, and higher molecular weight aliphatic carboxylic acids such as lauric, stearic, oleic acid or the salts of the esters mentioned with inorganic or organic acids. These compounds can be obtained according to the method of French patent 669,517. The quaternary ammonium bases, such as trimethyloctylammonium hydroxide, T ripropyllaurylammonium hydroxide, diethylphenylcetylammonium hydroxide, trimethyloleylammonium hydroxide, and the hydrochlorides, e.g. B. Dimethylphenylbenzylammoniumchlorid, also bromides, iodides, sulfates, acetates of the bases mentioned. These quaternary amnionium compounds can, according to the in Richte rA nschütz, Chemistry of Carbon Compounds, Vol. I, 1z. Aufl. (19z8), p. 2.7 under d., Specified processes. Furthermore, the salts of higher molecular weight aliphatic amines or their substitution products, eg. B. Laurylamine hydrochloride, Dimethyloleylaminliydrobromid, as well as the reaction products of haloparaffins with ammonia (cf. German patent 521 622) or mono- or polyamines (cf. French patent 7o9626) or condensation products of higher molecular weight fatty acids and amines (cf. z. B. B. French patent 669 517) and alkylated alkylenediamines (cf. German patent ._j.09 780 and French patent 595 67z).

The pretreatment is expediently carried out in an aqueous solution with an ordinary one or elevated temperature. It can be in neutral, acidic or alkaline liquor be made. You can also use the compounds mentioned in organic solvents Use dissolved for the pretreatment of the fibers.

The process described can be used for dyeing of all types of use animal fibers, e.g. B. for dyeing wool, silk or those containing Textiles, as well as hair. Leather can also be used at the usual, below boiling point lying temperatures using less than the usual amounts of acid dye with the addition of the named sticks: fabric compounds.

Deliver the fibrous materials pretreated in the manner described deep and even colors.

If the nitrogen bases are added to the dyebath, dyeing can take place using relatively low temperatures at normal or lower Acid concentration honing can be carried out. You get deep and lively, clear Colorations. The use of the nitrogen compounds mentioned is particularly advantageous Home dyeing with metal complexes from acidic wool. I'm multiple it is used to achieve even penetration of the material to be dyed and more flawless Dye liquors expedient in the pretreatment with the nitrogen compounds or when dyeing in the presence of nitrogen compounds, distributing agents with protective colloids Properties or water-soluble organic solvents or other substances too use. Furthermore, other additives are suitable as solvents, such as ethyl alcohol, Glycol ethers, polyglycol ethers or polyglycerines, polymeric ethylene oxide and pyridine. Inorganic salts, in particular alkali metal phosphates, can also be used as further additives or alkalis, water glass, which have a swelling effect on the fiber to be dyed, as well as also use oxylalkylamines.

The procedure can also be carried out advantageously using preparations carry out which the nitrogen bases, the dyes and optionally the distributing agents with protective colloid properties contained in color-coordinated amounts.

It has already been proposed to use animal fibers with metal complex compounds of acidic dyes in baths to color the water-soluble protective colloids and contain about such amounts of sulfuric acid as are generally more common for dyeing acidic dyes can be used. The protective colloids proposed for this, like glue and by introducing polyglyl; oil chains with at least four C., H, Compounds containing groups in oxy, carboxyl or amino groups Substances cause the dyebaths to foam. The present avoids this disadvantage Procedure. With the latter, there is also no matting of the material to be dyed, which is special when dyeing loose material is undesirable and when using compounds easily occurs with polyglycol ether chains with at least four C_H, -U groups; in the end a more even coloration is achieved than with the addition of glue.

The liquor ratio in the following examples is 1: 50. Example 1 for 'a liquor containing per liter roduktes 3- Einwiriz of n from a to 3: contains 11o1 ÄtlivIenoxyd on i mol Dodecyläthanolamin is treated ITerinowollgarn i hour at 6o- C . The yarn is then dyed with 2.5% victoria ruby (Schultz, Dyestuff Tables. 1931, = \ 'r. 2 i2) with the addition of 10% watric acid sulfate and 5% acetic acid for one hour at 60 ° C. Man obtained in this way a beautiful deep red color.Example 2 Wool is pretreated with a liquor which contains 3 g of trimethyldodecylammonium bromide per liter and then with 3% wool green BS (Schultz, Farbstofftabellen, 1931, No. 836) with the addition of 100% / 0 Glauber's salt, 5% acetic acid and 10% formic acid dyed for 1 hour at 60 ° C. A deep blue-green, very rubfast dyed product is obtained.

You dye not pretreated wool with the addition of i g of the formate of the triethanolamine monostearic acid ester per liter of liquor or the corresponding Amount of the amine mentioned in example i with 20/0 sorbin red (Schultz, color tables, 1931, no. 105) at 60 ° C under otherwise identical conditions, a deep red color is obtained Coloring with good rub fastness.

Example 3 A wool cheviot, which in a bath, which per liter i g des Contains formate of triethanolamine monostearic acid ester, pretreated at 60 ° C has been, is at 90 ° C with 0.40 / 0 of the complex chromium compound of the azo dye from diazotized 4-chloro-2-amino-i-oxybenzene-6-sulfonic acid and i-phenyl-3-methyl-5-pyrazolone (cf. German patent specification 455 277, example 3) and o, 20 / ö of the complex chromium compound of the azo dye -from diazotized i-amino-2-naphthol-4-sulfonic acid and 2-oxynaphthalene (cf. German patent specification 44i 867, example i) with the addition of 80/0 sulfuric acid colored. A very evenly colored product is obtained.

Example 4 Merino wool yarn is treated for 1 hour at 40 ° C. in a bath containing 3 g of trisodium phosphate and 0.5 g of octodecylpyridinium bromide (cf. British Patent 379396, Example 3) per liter and then with 2.5% victoria ruby , o, ro 0/0 sodium sulfate, 5% acetic acid (300/0) and 10/0 formic acid (850/0) for 1 hour at 60 ° C. A vivid red color is obtained.

Example 5 Merino wool yarn is in a liquor at 70 ° C. for 1 hour with 20/0 real light yellow 3 G (Schultz, Dye Tables, 1934 No. 732) with an addition of 0.3% of the product of action of about 3 moles of ethylene oxide to 1 mole of oleylamine colored. Well-dyed wool is obtained; the coloring is deep and very rub-proof. Example 6 Merino wool yarn is in a liquor for 11/2 hours at 80 ° C colored, the 3 0/0 ChromotropFB (Schultz, dye tables, 193z, no. 2o8) and 0.3% of the product of action of about 1 mole of ethylene oxide to 1 mole of heptadecylamine (cf. German Patent 552: 268). The color is then developed 3/4 hours at the cook; temperature with the addition of 10/0 potassium chromate and is obtained such a deep, rub-fast blue color.

Example 7 Merino wool yarn is made with 40% of the complex chromium compound of the azo dye from diazotized i-amino-2-oxynaphthalene-4-sulfonic acid and 2-oxynaphthalene (see German patent specification 441 867, example i) with the addition of 10/0 sulfuric acid and o.30% des Product of the action of about 5 moles of ethylene oxide on 1 mole of heptadecylamine for 1/2 hour at 80 ° C. A deep blue color is obtained. The dyeing can also be carried out in the same way with the addition of only 5% sulfuric acid, with the simultaneous use of 0.301 of the additive mentioned and 0.5% of the product of action of 25 moles of ethylene oxide on 1 mole of octodecyl alcohol or octodecylamine Receives colorations.

Example 8 Pieces of worsted yarn are dyed with 20/0 sorbine red (Schultz, Farbstofftabellen, 1934 No. 105) with the addition of 0.2% dodecyl diethanolamine and 0.3 % of the sodium salt of benzylnaphthalenesulfonic acid at 60 ° C. for one hour. A very even, deep color is obtained.

Instead of sodium benzylnaphthalenesulfonic acid, one can also use the product of action of 20 moles of ethylene oxide on 1 mole of the monoamide from lauric acid and ethylenediamine for a similar result.

Claims (5)

.PATENT CLAIMS: i. Method for dyeing animal fibers with acidic dyes, optionally containing metal in a complex bond, thereby characterized in that the dyed material from the usual acidic dyebaths with a content of water-soluble or water-displaceable nitrogen bases Trivalent or pentavalent nitrogen, which react with the dyes and at least an aromatic radical or an aliphatic radical with at least 6 carbon atoms, but no sulfonic acid groups or polyglycol ether chains with more than 3 glycol residues contained in the molecule, or after treatment with solutions of such nitrogen bases from the customary acidic dye ribbons below the boiling point colors. 2. The method according to claim i, characterized in that one dyeing using less than normal amounts of acid. 3. Procedure according to claim 2, characterized in that leather is, as usual, below the boiling point, however, using less than the usual amounts of acid and adding of the nitrogen compounds mentioned stains. Method according to claim z to 3, characterized characterized in that the said nitrogen bases are used together with distribution agents, which have protective colloid properties are used. 5. The method according to claim i to q., characterized in that dye baths are used which contain preparations have been ordered, which the dyes, the nitrogen bases and optionally the distribution agent with protective colloid properties in color coordinated Quantities included.