DE2615759A1 - PROCESS FOR AFTER-TREATMENT OF NITROGEN FIBER MATERIALS COLORED WITH REACTIVE DYES - Google Patents

Description

ClBA-GElGY AG, Basel, Switzerland V / S 'w *>''"J~~" ^^ ^ ί V _- JI

Germany

Process for the aftertreatment of nitrogen-containing fiber materials dyed with reactive dyes,

From the German Auslegeschrift 1 099 494 is a process for finishing dyeings on nitrogen-containing Known fibers. The dyeings are done in acidic, aqueous dyeing fabrics with soluble dyes, At least one that is mobile and reactive with the fibers Contain halogen atom, produced and the completion then takes place in such a way that one the pH of the Dye bath increased to over 6, in particular to 6.5 to 8.5, when the fibers have absorbed the desired amount of dye to have. This post-treatment fixes the dye on the fibers and thus the authenticity of the Coloring improved.

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Another method for fixing dyes is known from German Auslegeschrift 2 104 348. Natural or synthetic polyamide fibers are dyed with reactive dyes using the exhaust method, whereby the dye preparations contain an alkali donor, e.g. sodium trichloroacetate, in addition to the reactive dye, which increases the pH value in the course of the dyeing process and thus causes an improved fixation of the dye. If necessary, the alkali donor can also first be added to the dye bath towards the end of the dyeing process.

In both of the processes described, the dyed fiber materials are rinsed, optionally neutralized and drying completed.

The fastness properties, such as the wash, sweat or, in particular, rub fastness, according to the known methods of aftertreated fiber materials are not satisfactory in all respects.

It has now been found that the fastness properties of nitrogen-containing dyes colored with reactive dyes can be improved Fiber materials can be improved by the customary exhaust process in an acid dye bath colored materials in the drawn-out dyebath, one after the other an inorganic or organic base, an organic one Acid and a reducing agent, an oxidizing agent and

h 0 9 > ■ '* 4/1 0 5 9

2G15759

optionally a softening agent can be added, treated and then by dewatering and drying completes.

The present invention therefore relates to a process for the aftertreatment of dyeings on natural ones nitrogenous fiber materials, which are

umionic
rem dyebath with N reactive azo dyes which contain, as reactive groups, radicals of a carboxylic acid having at least one mobile halogen atom and / or a multiple bond capable of addition, vinyl sulfone groups or groups which form under the given dyeing conditions or the radical of an aromatic nitrogen heterocycle with two ring heteroatoms and at least one mobile halogen atom are, characterized in that the dyed fiber materials in the drawn out aqueous dye bath in one bath, but in stages one after the other

(a) at 70 to 80 ⁰ C in an aqueous liquor with a pH of 8 to 9,

(b) at 55 to 65 ° C with a reducing agent and a pH of the liquor of 4.5 to 5.5,

(c) at the same temperature with an oxidizing agent to remove the excess reducing agent,

• 'and if applicable

(d) Treated at 30 to 40 ⁰ C with a softening agent and then finished by dewatering and drying. B ₀₉₈₄₄ Z ₁₀₅₉

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The post-treatment process according to the invention can be used for dyeing on any natural, nitrogen-containing fiber materials, in particular on wool, and preferably can be used on wool with a felt-proof finish.

Under the strict washing conditions that apply to felt-resistant fiber materials, especially wool, the colorations are practically not changed due to the improvements in fastness achieved.

When fastening wool to the felt, a distinction is made between oxidative and additive (treatment with a synthetic resin) treatment processes, these methods also being combined in any order and possibly also simultaneously can be carried out.

In the oxidative process, e.g. peroxymonosulphuric acid, Potassium permanganate, chlorine or chlorine-releasing Use compounds such as di- and trichloroisocyanurate, usually a reduction step with, for example, sodium hydrogen sulfite to remove any unreacted oxidizing agents.

Far more important, however, are the processes in which the wool is treated with an oxidizing agent such as chlorine or a chlorine-releasing agent, is pretreated and then finished with a synthetic resin. Suitable synthetic resins that Cationic polyelectrolytes, i.e. polymers with a Numerous cationically ionizable sites, such as amine

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or amide groups.

For example, US Pat. No. 3,300,406 describes polymers with a main chain consisting exclusively of carbon atoms, to the units of the formula

(1) -C

are bonded, where A is alkylene having 2 to 3 carbon atoms. Such polymers can be made by reacting a di- or polyamine with a polymer of a monomer containing nitrile groups (acrylonitrile). A a particularly preferred polymer is, for example, a polyvinylimidazoline,

Another polymer that can be used to make felt resistant is a polyamide from AdipinsMure and diethylenetriamine, which is partially crosslinked with epichlorohydrin (British Patent 865 727). The essential cationic functional groups in the polymer are azetidinium chloride groups the formula

Cl "

(2) -N ^ CHOH

'CH ₂

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Others for the combined felt equipment suitable polymers are, for example, polyvinylpyridines, polypropylene polyamines, polyacrylamides, which are methylolated can be, polyamide-epoxy reaction products or mixtures made of polyamides and epoxies. The epoxides can be bisphenol A epichlorohydrin resins, while the polyamides can be made from fatty acids and polyalkylene polyamines.

Felt-proofing of wool without an oxidative pretreatment can also be done with reactive polyolefins, certain Polyurethanes, reaction products of epoxies with fatty amines and dicarboxylic acids or polyamides and in particular with polymers containing thiol end groups. These polymers with thiol end groups (polymercaptans) are e.g. conversion products

Polyalcohols, alkylene oxides with thioacids, such as those from U.S. Patent 3,645,781 are known. If appropriate, these polymercaptans can also be used together with others, in particular nitrogen-containing condensation products such as polyamine-epichlorohydrin Apply resins. The felt-proof finish is carried out according to known methods, essentially by padding the wool with aqueous solutions or emulsions of the specified polymers at 10 to 50 ° C, preferably at room temperature. The wool can also use oxidizing agents in the process as piece goods, i.e. as woven and knitted fabrics in other processing states, such as ais xose wool, Sliver or yarn are present. 609844/105 9

The anionic reactive azo dyes used for dyeing nitrogen-containing natural fiber materials are used expediently water-soluble dyes into consideration. Preference is given to dyes whose anionic character is due to the formation of metal complexes alone and / or by acidic salt-forming substituents is conditional. Such acidic groups are carboxylic acid groups, acidic sulfuric acid and phosphoric acid ester groups, Phosphoric acid groups, acylated sulfonic acid amide groups, such as alkyl or aryl disulfimide or alkyl or aryl carbonyl sulfimide groups and especially sulfonic acid groups. Particularly good results are achieved in the generally · achieved with dyes which have at least one sulfonic acid group.

The anionic reactive azo dyes can be metal-free, metallizable or heavy metal-containing mono-, bis- and polyazo dyes.

The reactive azo dyes can contain, for example, the following reactive groupings: the remainder of at least one a mobile halogen atom and / or an additive multiple bond containing acid, for example chlorine or Bromoacetic acid, ß-chloro and β-bromopropionic acid, cc, β-di-

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bromopropionic acid, tetrahalocyclobutanecarboxylic acid, such as 2-chloro-2-fluoro-3,3-difluoro- or 2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid, Propiolic acid, acrylic acid, methacrylic acid, α-chloro, ß-chloro, α-bromo and ß-bromo acrylic acid, α, β- and β, β-dichloro or dibromoacrylic acid, trichloro or Tribromoacrylic acid, 2- (2,2,3,3-tetrafluorocyclobutyl-1) acrylic acid, Crotonic acid, α- or ß-chloro or bromoerotonic acid, α, ß-dichlorocrotonic acid, vinylsulfonic acid, ß-chlorovinylsulfonic acid or a remainder of the dyeing conditions given can form a reactive vinyl sulfone group, such as β-hydroxyalkylsulfonyl-, esterified with strong acids, sulfonamido or carbonamido groups, such as the ß-haloethylsulfonyl, ß-Sulfatoäthylsulfonyl-, ß-Sulfatoäthylsulfamoyl-, ß-sulfatoethyl-N-methylsulfonamide or ß-sulfatopropionamido group; the ß-alkyl or ß-phenylsulfonylalkylsulfonyl, sulfonamide or carbonamide group, e.g.

the ß-phenylsulfonylpropionamido group. Reactive dyes with these reactive groups mentioned, in particular vinyl sulfone groups or such forming groups are preferred. Furthermore, the reactive group from the remainder of an aromatic Nitrogen heterocycle with advantageously two ring heteroatoms, which preferably contain at least one mobile halogen atom, such as fluorine, chlorine or bromine, or an acryloyl, N-hydroxymethyleneamino, sulfonic acid or alkylsulfonyl group, having bonded to a ring carbon.

Examples of such reactive groups are

6098AW10 5 9

2 61 b? 5 9

called: Diazinyl radicals with at least one mobile halogen atom, e.g. halopyrimidine or halopyrimidinecarboxylic acid radicals. In particular, di- or trihalopyrimidyl radicals, such as 2,4-di- or, in particular, 2,4,5-trichloro, bromo, fluoropyrimidyl radical or the 5-bromo-2,4-dichloro-pyrimidyl-6 radical called.

Other possible reactive groups are, for example, the remainder of 2,3-dihaloquinoxaline carboxylic acid or sulfonic acid, 2-halogen or 2-methylsulfonylbenzothiazole or oxazole carboxylic acid or sulfonic acid, 1,4-dihalophthalazine carboxylic acid, 2,4-dihaloquinoxaline carboxylic acid or 4,5-dihalo-6-pyridazon-l-yl-alkylene- or -phenylenecarboxylic acid, such as the acid residues of 2,3-difluoro- or 2,3-dichloroquinoxaline-6-carboxylic acid or -6-sulfonic acids 2- Chlorobenzothiazole or oxazole-5- or -6-carboxylic acid or -5- or -6-sulfonic acid; 1,4-difluoro-, 1,4-dichloro- or 1,4-dibromophthalazine-6-carboxylic acid or -6-sulfonic acid; 2,4-dichloroquinazoline-6- or -7-carboxylic acid, 2,3-dichloroquinoxaline-7-carboxylic acid or -7-sulfonic acid, 4,5-dichloro-6-pyridazon-1-yl-trimethylene carboxylic acid or -I ¹ , 4'-phenylenecarboxylic acid; also trichloropyridazinyl, S-chloropyridazine-o-carboxylic acid,

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As a rule, the dye baths can contain one or more nonionic and / or nonionic dyes in addition to the reactive dyes contain anionic surfactants.

Sulfated surfactants, for example, can be used as anion-active surfactants Addition products of 1 to 10 mol of ethylene oxide with higher fatty acids, higher aliphatic alcohols and alkylphenols, whose alkyl chain contains 8 to 20 carbon atoms, furthermore alkyl sulfonates with 10 to 20 carbon atoms in the Alkyl chain, alkyl benzenesulfonates with straight or branched ones Alkyl chain with 8 to 20 carbon atoms in the alkyl chain, such as nonylbenzenesulfonate, 1,3,5,7-tetramethyl-octylbenzenesulfonate or octadecylbenzenesulfonate, and also alkylnaphthalene sulfonates, for example bis-naphthyliuethanesulfonate or sulfosuccinic acid esters, such as sodium dioctyl sulfosuccinate, into consideration.

Nonionic surfactants are, for example, polyglycol ethers alkylated phenols with at least 7 carbon atoms in the alkyl chain and 4 to 30 alkyleneoxy groups, also N-acylated alkanolamines, .7ie the N, N ~ bis-hydroxyethylamides or Ν-γ-hydroxypropylamides higher Fatty acids with 10 to 20 carbon atoms, such as lauric,

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Myristic, palmitic, stearic or oleic acid or coconut fatty acid mixture, or also alkyl polyglycol ethers with 10 to 18 carbon atoms in the alkyl chain and 5 to 20 Ethyleneoxy groups and basic nitrogen atoms Polyglycol ethers, such as products obtained by reacting 1 mole of an amine with 3 to 100 moles of an alkylene oxide are, for example, the reaction product of 1 mole of dodecylamine.

Other customary additives can include electrolytes, acids, bases, urea, thiourea, thiodi'äthylenglykol and hydrophilic compounds with limited water solubility, such as butyl or benzyl alcohol.

The amounts of the substances to be added to the dyebaths can fluctuate within relatively wide limits. The amount of dye depends on the desired color strength and is generally between 0.1 to 8%, based on the fiber weight. The nonionic or anionic surfactants and other auxiliaries are generally used each in amounts of 0.01 to 4 percent by weight, preferably 0.1 to 1.5 percent by weight, based on the fiber weight, used.

The natural nitrogen-containing fiber material, in particular keratin-containing fiber material and preferably Wool, which is optionally made felt-proof, can be dyed in a manner known per se using the exhaust process, a liquor ratio of about 1:10 is expedient up to 1:40 and a pH value of the liquor of about 2.6 to 6, preferred

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wise 4 to 6, selects. The dye liquor with the material to be dyed without dye is advantageously allowed to run for about 10 to 30 minutes at 20 to 40 ^° C., then the dye is added and the temperature of the dyebath is increased within 50 to 70 minutes Cooking temperature and colors for 45 to 90 minutes at this temperature.

This is followed by the one-bath according to the invention, running over several stages, of the dyed fiber material in the practically drawn-out dyebath by cooling the dyebath to 70 to 80 ⁰ C, preferably to SO ⁰ C, and by adding inorganic or organic bases the pH of the Adjusts the liquor to 8 to 9, preferably 8 to 8.5.

Suitable inorganic bases are, for example, ammonia, alkali metal carbonates or bicarbonates, in particular Sodium and potassium carbonate or bicarbonate or alkali metal tho- or polyphosphates are used. The organic bases are essentially nitrogen-containing ones Bases, such as low molecular weight alkyl or alkanolamines with up to 4 carbon atoms in the alkyl or alkanol part, in particular around mono-, di- and triethanolamine.

After this first treatment stage of the post-treatment procedure, which takes about 10 to 20, preferably 15 minutes

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can take, the liquor is cooled further, for example by adding cold water. At 55 to 65 ° C, preferably at 60 ⁰ C, then, the addition of a reducing agent in the organic with an acid, preferably a low molecular weight organic acid having 1 to 4 carbon atoms, such as formic, acetic or oxalic acid, to a pH -Value of 4.5 to 5.5, preferably to a pH of 5, adjusted liquor. The reductive treatment serves in particular to destroy the dye detached from the fiber in the first stage - since it is not fixed - in order to prevent redeposition on the dyed fiber material.

Particularly suitable reducing agents for this purpose are the alkali dithionites, in particular sodium dithionite (Na ₂ S ₂ O,). The reductive treatment can also last 10 to 20, preferably 15, minutes.

In a third stage, the excess reducing agent is removed by oxidation, the dyed material being treated in the liquor for about 10 to 20 minutes at the same temperature. A particularly suitable oxidizing agent for this purpose is hydrogen peroxide (H ₂ Oo). The amount of hydrogen peroxide is about 0.5 to 1 ml (35%) per liter of liquor. The treatment time is about the same as specified for the previous stages.

Ansehliessend the liquor is heated to about 30 to 40 ° C, preferably about 4O ⁰ C, cooled, and the dyed material in a fourth optional step with a conventional softener

fi (J 9? ■: 4 4/1 Ω 5 9

treated to - if necessary - improve the soft hand of the dyed fiber material. The duration of treatment is also here about 10 to 20, preferably 15 minutes, and is carried out at the specified liquor temperature of 30 to 40.degree.

Suitable softeners are e.g. oil,

Fat and wax emulsions, fatty acid condensation products or also polyethylene, polyethylene glycol, siloxane and Silicone oil emulsions. If appropriate, mixtures can also be used of the softening agents mentioned are used.

Fatty acid condensation products that can be used are, for example: fatty acid methylolamides, optionally reacted with thioglycolic acid or aminoplast precondensates, Fatty acid-polyalkylenepolyamine reaction products, if appropriate reacted with ethylene oxide or other epoxides or epoxy reaction products or ammonium salts of Fatty acid-polyalkylenepolyamine condensation products. the Fatty acids contain 12 to 24, preferably 16 to 22 carbon atoms, and are e.g. lauric, myristic, palmitic, Stearic, arachidic or behenic acid.

The softening agents are preferably added to the extracted liquors in emulsified form. The emulsions for softening agents can contain about 10 to 30 percent by weight of active substance. The application amount for a 20%

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ige emulsion is about 0.5 to 4 percent by weight, based on the weight of the fiber material.

Mixtures of softeners, for example, are particularly suitable for example 50 to 80 parts by weight of a polyethylene (contains partially oxidized carboxyl groups) and 20 to 50 parts by weight a condensation product of dimerized unsaturated fatty acids and polyalkylene polyamines, e.g. Diethylenetriamine and triethylenetetramine or 50 to 80 parts by weight of said polyethylene, 10 to 30 parts by weight of paraffin (melting point range 50 to 75 ° C) and 10 to Contain 20 parts by weight of the condensation product mentioned. The dimeric unsaturated fatty acids can for example derived from unsaturated fatty acids containing 16 to 22 carbon atoms; preferably one uses linoleic, linolenic, Eleostearic or clupanodonic acid.

After this single-bath, but multi-stage post-treatment, the fiber material is dewatered and dried. As a variant of the aftertreatment process described, an aqueous rinsing bath can optionally be switched on after the treatment in the alkaline liquor (stage (a)) in order to rinse the fiber material at room temperature. The aftertreatment according to steps (b) to (d) is then continued in a ^{liquor at about 60 ° C.} This activated splicing process can further improve the fastness to use (rub, perspiration and wash fastness) of wool dyeings on materials that have not been pretreated, for example those that are not made felt-proof.

60984W 1 059

2615753

The result is dyeings with very good wet fastness properties and significantly improved rub fastness properties compared to the Dyeings that are only subjected to the usual ammonia aftertreatment have been.

Further advantages of the process according to the invention are the saving of water by working in a single bath and not a new set of equipment for each treatment stage must use. Furthermore, the process can be significantly reduced by a subsequent flushing process is no longer necessary; At the same time, this also saves a lot of water and accordingly less wastewater is produced. The amount of water required for rinsing is about 2 to 4 times the amount of water in the dyeing and post-treatment bath is used. With the method according to the invention, the amount of dyeing waste water can be marked be reduced.

In the following, first the regulations for the felt equipment and the dyeing process are given, then the exemplary embodiments for the aftertreatment process according to the invention follow.

Parts and percentages are given as parts and percentages by weight.

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Felt fixation

A. A 50 cm wide horizontal foulard is adjusted to have 20 combed slivers with a middle Can handle a weight of 20 g / m and runs at a speed of 5 m / min, with a 120% uptake of the Solution based on the weight of the train is obtained.

Two solutions are prepared as described below, the percentages being percentages by weight mean.

Solution 1 solution 2

5% sodium dichloroisocyanurate 1.0% sulfuric acid

1 % polyethyleneoxyalkylene phenol 0.8% polyvinylimidazoline

0.7 % morpholine (stabilizer)

Temperature = 20 ⁰ C temperature = 20 ⁰ C

pH = 6.3 pH = 1.6

The solutions (1) and (2) are mixed in a volume ratio of 1: 1 and added to the padding liquor (pH value: 2.4). During the process, the padding liquor is continuously added by adding more of the solutions (1) and (2) kept at a constant volume. After padding, the tops are left in a collecting box for 10 minutes.

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before he is directed in a lisseuse for further treatment in the following solutions:

a) aqueous rinsing bath 20 ° C

b) solution containing 4% sodium sulfate, 1 % sodium bisulfite, pH 7.6, 25 ° C. This bath is kept at a constant level by adding 15% sodium sulfite solution.

c) aqueous rinsing bath.

The tops are then dried.

The sliver was spun and made into one piece knitted, which shows a good felt-proof effect.

B. A woolen fabric (100% wool) is impregnated with the following aqueous liquor at room temperature:

90 parts of polythiol A (40% strength aqueous emulsion) 12 parts of condensation product I (20% strength aqueous emulsion)

Solution)

2 parts of adduct of 9 mol of ethylene oxide and 1 mol of ρ-tert-nonylphenol (75% aqueous Solution)

20 parts of sodium carbonate
876 parts of water

1000 parts

The fabric is padded and weight gain 80%

6 0 9 B h UI 1 0 5 9

squeezed off, then it is dried ^{at 110 to 130 ° C. for 2 to 4 minutes.}

Polythiol A:

A mixture of 800 g (0.2 g / mole) of a thiol with an average molecular weight of 4,000 was prepared from glycerine and propylene oxide, 55.2 g (0.6 g / mol) thioglycolic acid, 5 g of toluene-p-sulfonic acid and 350 ml of toluene is under Stir to reflux in a nitrogen atmosphere. The water formed during the reaction (10.8 ml, 0.6 g / mol) is removed as an azeotrope with toluene. the The mixture is cooled and washed with water and the organic layer is separated. After removing the solvent of the organic layer under vacuum, 793 g (theoretical yield 94%) of the desired tris (thioglycolate) remain with a thiol content of 0.59 equivalents /. kg back.

The emulsions containing the polythiol are prepared by dissolving 0.5 part of sodium arboxymethylcellulose in 44.5 parts of water at 70 to 80 ^° C., allowing the solution to cool, adding 50 parts of the polythiol and 5 parts of a wetting agent (an adduct of p-nonylphenol and 9 moles of ethylene oxide) and stirring for five minutes in a high-speed mixer.

6 0 9 ft k 4/1 0 5 9

Condensation product I:

3 moles of diethylenetriamine are heated first with 1 mole of dicyandiamide and then with 2 moles of dimethyl adipate. This reaction product is then heated with 4.5 moles of epichlorohydrin, and the resin is finally diluted with water so that a 20% strength solution of the condensation product I is obtained.

C. Woolen sliver is in a sulfuric acid aqueous Liquor (pH value: 2) pretreated with sodium hypochlorite in such an amount that there is 1% chlorine on the Fiber is located.

The chlorinated wool is then treated with a solution of 6 g / l sodium bisulfite and then with a solution treated by 9 g / l sodium hydrogen carbonate, then rinsed well in cold water and dried.

The wool is then mixed with 8.5 g / l of a 10X aqueous solution of a polyamide-epichlorohydrin resin (made from adipic acid, diethylenetriamine and epichlorohydrin) padded and weight gain of 100% squeezed off, then dried and cured for 10 minutes at 85 ° C. and finally finished by rinsing and drying

D. Dyeing method:

Ready-made knitwear or yarn made from undyed wool, which is felt-free as a top, (method

6 0 9 ο 4 U / 1 0 BS

A or C) or appropriately finished woolen fabrics (method B) are in an aqueous liquor (liquor ratio 1:35 to 1:40) colored as follows:

In the liquor are at 20 ⁰ C

2% ammonium sulfate,

1% of a reaction product of 1 mol of fatty amine and 7 mol of ethylene oxide, quaternized with chloroacetamide (54% aqueous solution), 1% of the ammonium salt of the acid sulfuric acid ester of the reaction product of 1 mol of fatty amine and 7 mol of ethylene oxide (547o aqueous Solution) and

Acetic acid (80%) to adjust a pH value of 4.5 to 5,

given. Allow the fleet with the dyed goods are pre-run for 15 minutes at 20 ⁰ C, then X% of a reactive dye added, heating the liquor in 50 minutes to 70 ⁰ C, leaving 15 minutes at this temperature, then heated in 30 minutes to boiling temperature (98 ° C) and stains at this temperature for 90 minutes. The percentages relate to the weight of the goods to be dyed.

For example, dyes of the following formulas can be used in the dye baths:

B 0 9 B U A / 1 0 5 9

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HOoS NH I CO I C-Br

CH NHCOC = CH,
Br

Red

CH ₀ = CCONH ² I Br

Red

SO ₉ H

N = N

/ Vn = N

SO ₃ H

NHCOCH ₂ Cl

SO ₃ H CH ₃ CH ₃

Scarlet fever

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F Cl

Red

/ Λ

CO-NH OH

(7)

N = N- ί

Red

(8th)

OH N = N

HO ₃ S

- SO ₂ CH ₂ CH ₂ OSO ₃ H

Red

60984 A / 1 0 59

2k -

example 1

Wool serge with a felt-proof finish according to method B is used with

a) 4.5% of the dye of the formula (3)

b) 4% of the dye of the formula (6) or c) 5% of the dye of the formula (7) dyed by the exhaust process (dyeing process D) and then in the practically exhausted dye bath as follows post-treated:

a) cooling the liquor to 80 ^° C.

Addition of 8% ammonia (24%), pH of the liquor 8.5

Treatment time: 15 minutes

b) Cooling the liquor by ^{adding cold water to 60 °} C., adjusting the pH to 5.0 by adding 80% strength acetic acid.

After about 5 minutes, 0.25 % sodium dithionite mixed with sodium pyrophosphate is added to the liquor. Treatment time: 10 minutes

c) Addition of 1 ml / 1 H ₉ O ₉ (35%). Treatment duration minutes. The liquor is then cooled to 40 ^° C. by the addition of cold water.

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d) Addition of 2% of an aqueous polyethylene emulsion (25%) (softener)

Treatment time: 15 minutes at 40 ^° C. The wool is then drained and dried.

The following fastness properties are checked:

- Alkaline sweat - SNV 195824/1961

The change in color and the staining of wool (WO-felt-resistant finish according to method C) and cotton (CO) determined. Grades 1 to 5 each.

- Washfastness - IWS ™ 193 (American Dyestuff Reporter 35 (1973); Determination of the change in color and staining as in the determination of the fastness to perspiration.

- Rubbing fastness - SNV 195831

Grades 1 to 5, with 5 being the best grade.

Table 1

colored
with
Color
material Alkaline sweat Bleeding CO Washfastness Bleeding CO Rubbing fastness wet formula
(3)
(6)
(7) Nuances
modification WHERE 5
4-5
4th Nuances
modification WHERE 5
4th
5 dry 4th
4th
4th 5
4-5
4-5 5
5
4th 4-5
4-5
3-4 5
5
5 4th
4th
4th

The results in Table 1 show that very good all-round fastness properties can be achieved.
The felt-proof effect is not negatively affected by the aftertreatment. _h qg ₈ / ₊ / * / 1 Q 5 9

Example 2

The after dyeing process D with 5% of the dye of the formula (3) present as strand yarn (made felt-resistant according to method A) is described as in Example 1 aftertreated and also tested for the fastness properties specified there.

For comparison, the aftertreatment is only carried out with ammonia or with ammonia and a soft handle, whereby a flushing process is connected.

Table 2

Alkaline sweat Bleeding CO Washfastness Bleeding CO Rubbing fastness wet post-treated
after
THE 1099494
(ammonia only) Nuances
modification WHERE 4-5 Nuances WHERE 5 dry 2 post-treated
with ammonia
and soft handle
middle 4-5 5 4-5 modification 5 5 5 2 inventive
after treatment
delt 5 5 5 4-5 5 5 4-5 4th 5 5 4th 5 5 5

β fj 9 b 4 Λ / 1 Q 5 9

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With the aftertreatment process according to the invention, a significant improvement in the rub fastnesses can be achieved (wet) can be achieved. Furthermore, the results for the wash and perspiration fastness properties show that the fastness properties are optimal the dyeings even without the very complex rinsing process at the end of the, which is necessary according to the state of the art Post-treatment can be achieved.

Example 3

400 g of worsted wool (not made felt-proof) is dyed with 5% of the dye of the formula (3) by dyeing process D in a rope dyeing machine and then aftertreated as described in Example 1. In a second post-treatment, a rinsing process in an aqueous liquor is carried out at room temperature and then with the step b) (liquor temperature after the step a) (ammonia treatment): 60 ⁰ C) to d) proceed. The liquor volume for the rinsing process corresponds to the volume of the dye liquor. The fastness properties specified in Example 1 are tested, the wash fastness being determined in accordance with SNV 195819, however.

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Table 3

Alkaline sweat Bleeding CO Washfastness Bleeding CO Rubbing fastness | wet post-treated
(according to At
game 1) Nuances
Change WHERE 4-5 Nuances
modification WHERE 4-5 dry 3-4
i post-treated
(with rinsing pro
process after
Stage a)) 5 5 5 5 5 5 4-5 !
4 ■ 5 5 5 5 4-5

The results show that with the rinsing process after stage a) of the post-treatment process, the already good General fastness properties, especially fastness to rubbing (wet), can be further improved.

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Claims (20)

Claims 1. Process for the aftertreatment of dyeings on natural nitrogen-containing fiber materials, which in ^ anionisehen acid dyebath with \ reactive azo dyes acting as reactive groups Residues of at least one mobile halogen atom and / or a multiple bond capable of addition Carboxylic acid, vinyl sulfone groups or groups which form under the given dyeing conditions or the Residue of an aromatic nitrogen heterocycle with two ring heteroatoms and at least one mobile halogen atom contain, have been produced, characterized in that the dyed fiber materials in the drawn one-bath aqueous dye bath, but in stages one after the other (a) at 70 to 80 ⁰ C in an aqueous liquor with a pH of 8 to 9, (b) at 55 to 65 ° C with a reducing agent and a pH of the liquor of 4.5 to 5.5, (c) at the same temperature with an oxidizing agent to remove the excess reducing agent, and if necessary (d) Treated at 30 to 40 ⁰ C with a softening agent and then finished by dewatering and drying. ß 0 9 i'h UI 1 0 5 9 2. The method according to claim 1, characterized in that dyeings on wool are aftertreated. 3. The method according to claim 2, characterized in that dyeings are aftertreated on wool with a felt-resistant finish. 4. The method according to claim 3, characterized in that dyeings on by oxidative processes and / or Post-treated with synthetic resin coating of wool with a felt-proof finish. 5. The method according to claim 1, characterized in that the pH of the liquor from 8 to 9 in step (a) with inorganic or organic bases. 6. The method according to claim 5, characterized in that the pH of the liquor from 8 to 9 in stage (a) with Ammonia, alkali carbonates or bicarbonates or alkali ortho- or polyphosphates is set. 7. The method according to claim 5, characterized in that the pH of the liquor from 8 to 9 in stage (a) with nitrogen-containing organic bases, especially alkyl or alkanolamines is adjusted. 8. The method according to claim 1, characterized in that the pH of the liquor from 4.5 to 5.5 in stage (b) with ß Ü 9 8 kk I 1 0 5 9 low molecular weight organic carboxylic acids with 1 to 4 carbon atoms is set. 9. The method according to claim 8, characterized in that the pH of the liquor from 4.5 to 5.5 in stage (b) with Formic or acetic acid is adjusted. 10. The method according to claim 1, characterized in that the reducing agent in step (b) is alkali dithionites begins. 11. The method according to claim 1, characterized in that the oxidizing agent in step (c) is hydrogen peroxide begins. 12. The method according to claim 1, characterized in that that as a softener in stage (d) oil, fat and wax emulsions, Fatty acid condensation products, polyethylene, polyethylene glycol, siloxane and silicone oil emulsions or mixtures thereof begins. 13. The method according to claim 12, characterized in that the softening agent in step (d) is mixtures of polyethylene with anoxidized carboxyl groups, condensation products. dimerized fatty acids, which differ from unsaturated Derive fatty acids with 16 to 22 carbon atoms, and polyalkylene polyamines and optionally paraffin and / or silicone oil is used. 609844/10 59 14. The method according to claim 12, characterized in that one fatty acid-polyalkylenepolyarain condensation products or their ammonium salts, which are derived from fatty acids with 16 to 22 carbon atoms, are used. 15. The method according to claim 12, characterized in that one condensation products of dimerized linoleic and Linolenic acid and diethylenetriamine or triethylenetetramine are used. 16. The method according to claim 12, characterized in that raan as We ichgriff means in step (d) a mixture 50 to 80 parts by weight of an oxidized carboxyl group-containing polyethylene and 20 to 50 parts by weight of a condensation product from dimerized fatty acids and diethylenetriamine is used. 17. The method according to claim 16, characterized in that the softening agent in step (d) is a mixture of 50 to 80 parts by weight of an oxidized carboxyl group-containing polyethylene, 10 to 30 parts by weight of paraffin and 10 to 20 parts by weight of a condensation product of dimerized fatty acids and diethylenetriamine are used. 18. The method according to claim 1, characterized in that the post-treatment of the colored fiber materials in each case , ''. / "ι ι ' ^l . ^f -i Takes 10 to 20 minutes for each of steps a) to d). 19. The method according to claim 1, characterized in that the fiber materials according to step a) one Subjecting to rinsing process in an aqueous liquor at room temperature and then according to steps b), c) and optionally d) further treated. 20. The dyeings obtained by the process according to claim 1 on natural nitrogen-containing fiber materials . FO 3.31 Mk / ma 609844/1059