EP0073883A2 - Method for the manufacture of non-felting wool - Google Patents

Abstract

It consists in a pretreatment of ecru wool in the presence of an oxidising agent and a subsequent application of a non-felting finish using a curable polymer with or without dyeing.

Description

The invention relates to a process for the production of wool which is finished without felt by pretreating raw white wool in the presence of an oxidizing agent and subsequent finishing with felt-free polymers and optionally dyeing.

A large number of processes for finishing felt-free articles from wool and wool blends with curable polymers are already known. These include processes that make it possible to achieve permanent felt-free effects such as are necessary for the production of machine-washable wool articles without prior chlorination.

By eliminating the pre-chlorination, the disadvantageous changes that can be attributed to this treatment stage can be avoided, such as a time-consuming and water-consuming pretreatment of the wool, yellowing of the wool, reduction of the levelness and fastness of dyeings, difficulties in the er setting of pastel tones and increasing the tendency to pilling.

Suitable polymers and the process are known from GB-PS 1 419 306, GB-PS 1 453 816, GB-PS 1 423 342, DE-PS 2 334 655 and DE-OS 2 837 851. Water-soluble curable polymers are preferred.

With the help of this method it is possible, for example, to knit parts made from raw white or colored yarns, such as wool sweaters, socks and stockings, after an alkaline wash or whale wash using a nonionic surfactant in a fresh bath containing an inorganic salt, for example magnesium chloride hexahydrate , and a prepolymer, e.g. a prepolymer polyurethane containing carbamoylsulfonate groups, to be finished without a felt.

Using this method, raw white or yarn-colored wool articles from a long fleet can be finished very well without felting. The felt-free effects meet the requirements that the International Wool Secretariat places on machine-washable wool articles that are to be labeled "Superwash". For this it is necessary that the articles are checked in a Cubex test device with a liquor ratio of 1:15 with a phosphate buffer solution of 40 ° C for 180 minutes, do not exceed the shrinkage values specified for individual articles.

However, it was found that the felt-free effects of raw white finished wool articles by a subsequent dyeing is reduced and thus the effectiveness of the felt-free finish originally corresponding to the Superwash standard is reduced to such an extent that this standard is no longer achieved.

The extent of the deterioration in effect depends on the type and amount of the leveling agent required for the dyeing and the dyeing time. Nonionic leveling agents, which are used when dyeing wool with reactive dyes, are particularly unfavorable. Amphoteric leveling agents, as are customary when dyeing with acid, post-chromium or metal complex dyes, are less unfavorable.

The reduction in effect can be compensated for by increasing the use amounts of the felt-free finishing agents. However, this increase leads to a significant increase in the cost of the equipment and a significant change in the handle failure towards the full, hard side. This change in the feel that is typical and valued for wool is no longer acceptable for knitwear made from fine lambswool, especially for items made from worsted.

The process according to the invention now allows raw white wool articles without pre-chlorination to be treated with reduced amounts of non-felting agents so that a machine-washable garment with a soft grip results after dyeing. Felt-free finishing and coloring can be in any order be carried out. Another advantage of the process according to the invention is that the dyeing of wool articles which are finished felt-free from the long liquor after the pull-out process can be carried out in the same bath after the felt-free finish, or that dyeing can be carried out from a fresh bath without intermediate drying.

However, even in the case of raw white articles which are not to be colored, the process according to the invention permits a reduction in the use amounts of the felt-free finishing agents and thus a softer grip failure.

It is also possible to use polymers which are not suitable for the finishing of raw white articles without pre-chlorination.

It has been found that this goal is achieved by adding an oxidizing agent, preferably hydrogen peroxide, to the pretreatment liquor (wash or whale wash liquor), which is preferably alkaline. The preferred concentration of hydrogen peroxide (35%) in the pretreatment liquor is 1-50 ml / l, in particular 10-20 ml / l.

Advantageously, the pretreatment liquor additionally contains a regulator that controls the delivery of active oxygen.

Suitable regulators are, for example, the substances known as stabilizers for peroxide bleaching, which have been described by A. Chwala and V. Anger in "Handbuch der Textilhilhilmittel" (1977) pp. 340 u. 341 can be described. These are silicates, poly- or pyrophosphates, borates, stannates, Mg salts of polyaminocarboxylic acids and fatty acid derivatives. Pyrophosphates such as tetrasodium pyrophosphate decahydrate are preferred. The preferred concentration in the pretreatment liquor is 0.2-10 g / 1, in particular 1-5 g / l.

The pretreatment liquor preferably contains nonionic products as surfactants, which are described, for example, by K. Lindner in "Tenside, Textilhilfsmittel, Waschrohstoffe" (1964), pp. 865-916. Examples of reaction products of alkylphenols, e.g. Nonylphenol, or alcohols, e.g. Oleyl alcohol, called with ethylene oxide or propylene oxide.

The preferred concentration is 0.5-5% by weight, in particular 1-3% by weight, based on the weight of the wool article.

The pH of the pretreatment liquor is preferably between 8 and 11, in particular 9 and 10. The pretreatment in most cases is a treatment time of 5-60 minutes, in particular 10-20 minutes, at 30-60 ° C., in particular 40-50 ° C sufficient. These conditions can easily be determined in individual cases by preliminary tests.

Curable polymers which can preferably be used in the process according to the invention are, for example, the bisulfite adducts of polyisocyanates known from GB-PS 1 419 306 and GB-PS 1 453 816.

Suitable isocyanate components are preferably aliphatic, cycloaliphatic or araliphatic polyisocyanates, such as, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, hexahydrotoluylene diisocyanate, 4,4'-diis, ocyanatodicyclohexylmethane, 5-isocyanato-5,5-1-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanato-5-isocyanate isocyanatomethylcyclohexane, p-xylylene diisocyanate or also urethane or biuret groups containing polyisocyanates, such as the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole of water. Aromatic diisocyanates such as p-phenylene diisocyanate, the tolylene diisocyanates and diphenylmethane diisocyanates are less preferred according to the invention. According to the invention, prepolymers containing NCO groups are preferably used according to the invention, such as are formed by reacting water or a polyhydroxyl compound with an excess of one of the polyisocyanates just mentioned. In this context, in addition to low molecular weight glycols and triols and polyester polyols, the polyols which are preferably di- or trifunctional polyhydroxy polyethers with a molecular weight between 500 and 10,000, in particular between 1,000 and 5,000, as can be obtained by alkoxylation of di- or trifunctional starter molecules, such as water, ethylene glycol, 1,2-propanediol, 1,3-propanediol, trimethylolpropane or glycerin in are accessible in a known manner. According to the invention, particular preference is given to polyether polyols made from propylene oxide.

The bisulfite adducts mentioned can also be used together with other curable polymers. Preference is given here to water-soluble or emulsifier-free dispersible polyurethanes having anionic groups, for example the polyurethanes described in GB Pat. No. 1,336,050 with an alkanesulfonic acid group.

Other curable polymeric substances which can be used in the process according to the invention are, for example, Bunte salt compounds from GB-PS 1 423 342 and polyethers containing aziridine residues from DE-PS 2 334 655.

worin n etwa 13 ist.Colorful salt compounds have a backbone of a polymer chain and at least two thiosulfate groups per molecule. The chain can in particular be a polyoxyalkylene chain, for example a polyoxypropylene chain. Particularly preferred compounds have the formula

where n is about 13.

in der R₁ bis R₇ Wasserstoff oder niedermolekulares Alkyl, Q den Rest eines n-wertigen Alkohols oder Phenols, n 2 oder 3, X eine Polyetherkette aus Butoxy- und/oder Propoxy- und gegebenenfalls Ethoxyeinheiten mit einem Atomverhältnis C : O von mindestens 2,67 : 1 und einem Molekulargewicht von 150 bis 1500 bei n = 2 und von 150 bis 3000 bei n = 3 bedeuten.Polyethers containing aziridine residues correspond to the general formula

in which R ₁ to R _{7 are} hydrogen or low molecular weight alkyl, Q is the residue of an n-valent alcohol or phenol, n 2 or 3, X is a polyether chain of butoxy and / or propoxy and optionally ethoxy units with an atomic ratio C: O of at least 2.67: 1 and one Molecular weight from 150 to 1500 when n = 2 and from 150 to 3000 when n = 3 mean.

Examples of suitable low molecular weight alkyl radicals are those having 1 to 3 carbon atoms, in particular methyl; however, the compounds with R ₁ to R ₇ = hydrogen are preferred.

The amount of polymeric material used is 0.5-10%, based on the weight of the wool article, preferably 1-4%.

The curable polymers can be applied by padding from a short liquor or by pulling out from a long liquor.

The liquor ratio for the felt-free finish from a long liquor is 10: 1 to 100: 1, in particular 20: 1 to 30: 1.

Wool is any type of animal hair (keratin fibers).

Woolen articles are to be understood as the various processing stages of wool, such as sliver, yarn, but preferably fabrics and knitwear, as well as knitted parts.

In principle, all wool dyes are suitable as dyes, the fastness properties of which meet the requirements placed on machine-washable articles the. Reactive dyes, metal complex dyes, post-chromium dyes and acid dyes may be mentioned.

example 1 Experiment 1 A:

250 g of raw white knitted parts made of Shetland wool yarn are placed on an overhead laboratory paddle in 10 liters of soft water (water up to 5 ° d) (liquor ratio 1:40), the 5 g (2%) of a nonionic detergent (mixture of

The liquor is drained and the goods are rinsed twice with warm water (about 30 ° C).

• Flottenmenge: 9,5 Liter;
• Flottentemperatur: 30°C.

The felt-free finish from a fresh bath is then carried out as follows:

• Fleet volume: 9.5 liters;
• Fleet temperature: 30 ° C.

By adding 1.5 g soda calc. the pH of the liquor is adjusted to 10. Then 80 g of magnesium chloride hexahydrate (technical), dissolved in about 500 ml of warm water are added.

Then there is the addition of 1.5%, based on the weight of the knitted parts, of the setting a (= 50% aqueous solution of a bisulfite-blocked NCO prepolymer according to GB-PS 1 453 816, Example 2) dissolved in about five times Amount of cold soft water and of 1.5%, based on the weight of the knitted parts, the setting b (= 40% anionic polyester-polyurethane dispersion according to GB-PS 1 336 050, example 4) diluted in about ten times the amount of cold soft water .

The pH is then around 8. The cloudy equipment liquor is heated to 60 ° C. (1 ° C./minute) within 30 minutes. During this heating-up period, the two finishing agents pull onto the goods, which is shown by a gradual decrease in the haze. At 60 ° C the fleet is almost water-clear.

In order to achieve a crosslinking of the drawn products on the wool, the treatment is continued at 60 ° C for 30 minutes.

The Shetland knitted pieces finished in this way are then dyed with reactive dyes in the same bath in the usual way without the addition of salt. For this purpose, 3% acetic acid (60%) is first added to lower the pH to 4.5-4.8. Then add 1.5% = 3.75 g of a nonionic leveling agent dissolved in about 20 ml of warm water.

After a short lead, the dissolved dyes are added:

The dye mixture is pasted with a little cold water and dissolved by pouring 100 ml of boiling water and stirring.

The mixture is then heated from 60 ° C to 100 ° C within 30 minutes and dyed at cooking temperature for 2 hours. The mixture is then cooled to 80 ° C. by adding cold water, the pH is raised to 8.5 with 80 ml of ammonia solution (25% strength) and the goods are treated at this pH for 20 minutes. By adding cold water in the overflow, rinsing is clear.

Finally, the goods are acidified in 10 liters of liquor containing 1% = 2.5 g of formic acid (85%) for 10 minutes and then rinsed.

The knitted parts are removed as usual, spun off, dried and briefly steamed.

To determine the felt-free effect, the knitted parts are relaxed in a Cubex washing machine in accordance with IWS test method 9 and the surface shrinkage is then determined in accordance with IWS test method 185. For this purpose, the material is treated for 3 hours in a Cubex washing machine in 15 liters of phosphate buffer solution with a pH of 7 at a total load of 1 kg (by adding additional pieces made of single-layer polyester tricot).

The knitted parts resulted in a flat felt shrinkage. of 13%. They therefore do not meet the IWS requirements for a maximum of 10% surface felt shrinkage.

In further experiments 1 B - 1 D, Shetland knitted parts of the same type and quantity are finished and dyed with increasing amounts of finishing agent using the procedure described in Experiment 1 A:

The tests of the shrinkage behavior according to the IWS test methods 9 and 185 mentioned gave the following values for the surface felt shrinkage:

In a further experiment 1 E, 250 g of Shetland knitted parts of the type used in Experiments 1A-1D are subjected to a whale wash in the manner described under Experiment A, with the difference that the wash liquor - apart from 5 g of the nonionic detergent and , 5 g soda calc. additionally contains 50 g tetrasodium pyrophosphate decahydrate (5 g / l) and 200 ml hydrogen peroxide (35%).

The felt-free finishing is carried out as described under test A.

The shrink test showed a surface felt shrinkage of 2.6%.

The following table is a summary of the test results:

From these values it can be seen that the pretreatment according to the invention was carried out in experiment 1 E for a user amount of 1.5% each at settings a and b enables as good a felt-free effect as an application amount of 3% of these products with normal whale washing.

Example 2 Experiment 2 A:

A woolen sweater made of raw white lambswool weighing 220 g is, after a chemical cleaning in perchlorethylene, as described in Example 1, test A subjected to a whale wash.

The liquor contains 1% of the non-ionic detergent and 5 g calc. Soda. The treatment time is 20 minutes at 45 - 50 ° C.

• 3 % der Einstellung a und
• 3 % der Einstellung c (= 40 %ige anionische Polyester-Polyurethan-Dispersion hergestellt durch Umsetzung eines NCO-Präpolymeren aus einem Adipinsäure/Hexandiol-Polyester (Molekulargewicht 1000), Butandiol und Hexamethylendiisocyanat mit der wäßrigen Lösung eines Gemisches aus Ethylendiamin und dem Na-Salz von Ethylendiamino-ethansulfonsäure analog GB-PS 1 336 050, Beispiel 4)

aufgebracht werden.The subsequent felt-free finishing and dyeing is also carried out according to Example 1, however

• 3% of setting a and
• 3% of the setting c (= 40% anionic polyester-polyurethane dispersion produced by reacting an NCO prepolymer from an adipic acid / hexanediol polyester (molecular weight 1000), butanediol and hexamethylene diisocyanate with the aqueous solution of a mixture of ethylenediamine and the Na Salt of ethylenediaminoethanesulfonic acid analogously to GB-PS 1 336 050, example 4)

be applied.

Experiment 2 B:

A lambswool sweater from the one used in Experiment 2A _A rt is subjected to the pretreatment described there, with the difference that, according to the invention, the alkaline whale wash liquor in addition to 1% of the nonionic detergent and 7.5 g of calc. Soda additionally contains 200 ml of hydrogen peroxide (35%) and 5 g / 1 tetrasodium pyrophosphate decahydrate. Felt-free finishing and dyeing correspond to test 2 A.

The improvement in the pretreatment according to the invention can be seen from the values for the surface felt shrinkage:

Example 3 Experiment 3 A:

A worsted wool sweater made of raw white lambswool weighing 280 g was, as described in experiment 1A, washed and equipped with 4% settings a and b each without felt; however, after reaching the bath temperature of 60 ° C, the pH was adjusted by adding 1 g / l calc. Soda set to 9 and further treated at 60 ° C for 30 minutes.

• 2 % -des blauen Farbstoffs der DE-AS 1 099 799, Beispiel 5,
  

in üblicher Weise durchgeführt. Färbedauer: 2 Stunden.The subsequent staining was done on a fresh bath

• 2% of the blue dye of DE-AS 1 099 799, Example 5,
  

performed in the usual way. Staining time: 2 hours.

Experiment 3 B:

Like experiment 3A, but the alkaline washing liquor (10 liters) contained 2% of the nonionic detergent from experiment 1A as in experiment 1U; 7.5 g calc. Soda, 200 ml hydrogen peroxide (35%) and 50 g tetrasodium pyrophosphate decahydrate.

Example 4

Material: raw white worsted wool sweater, weight 270 g

Filzfreiausrüstung: wie Versuch 1 A aber mit je 3 % Einstellung a und b.Pretreatment:

Felt-free equipment: like experiment 1 A but with 3% settings a and b.

Coloring in the same bathroom

Example 5

Material: as example 4

Pretreatment: 10 minutes at 45 ° C

• Versuch 5 A: wie bei Versuch 3 A
• Versuch 5 B: wie bei Versuch 3 B

Pretreatment fleet:

• Experiment 5 A: as in experiment 3 A
• Experiment 5 B: as in experiment 3 B

_F ilzfreiausrüstung: as in Experiment 1 A, but B with 4% and a setting.

Coloring as in experiment 1A

Test 5 A: 23.7% surface felt shrinkage Test 5 B: 2.6% "

Example 6

Material: raw white worsted wool knitwear Quantity: 250 g per test Pretreatment: 20 min. At 50 ° C

• Versuch 6 A: 1 % des o.g. nichtionogenen Waschmittels 1 g/l calc. Soda
• Versuch 6 B: 1 % des o.g. nichtionogenen Waschmittels 1,4 g/1 calc. Soda 20 ml/1 Wasserstoffperoxid (35 %ig) 5 g/1 Tetranatriumpyrophosphat-Dekahydrat
• Versuch 6 C: 1 % des o.g. nichtionogenen Waschmittels 1,8 g/l calc. Soda 20 ml/l Wasserstoffperoxid (35 %ig) 1 g/l Tetranatriumpyrophosphat-Dekahydrat
• Versuch 6 D: 1 % des o.g. nichtionogenen Waschmittels 1 g/1 calc. Soda 5 ml/l Wasserstoffperoxid (35 %ig) 1 g/1 Tetranatriumpyrophosphat-Dekahydrat
• Versuch 6 E: 1 % des o.g. nichtionogenen Waschmittels 1 g/1 calc. Soda 1 ml/1 Wasserstoffperoxid (35 %ig) 0,2 g/l Tetranatriumpyrophosphat-Dekahydrat

Treatment fleet:

• Experiment 6 A: 1% of the above-mentioned nonionic detergent 1 g / l calc. soda
• Experiment 6 B: 1% of the above-mentioned nonionic detergent 1.4 g / 1 calc. Soda 20 ml / 1 hydrogen peroxide (35%) 5 g / 1 tetrasodium pyrophosphate decahydrate
• Experiment 6 C: 1% of the above-mentioned nonionic detergent 1.8 g / l calc. Soda 20 ml / l hydrogen peroxide (35%) 1 g / l tetrasodium pyrophosphate decahydrate
• Experiment 6 D: 1% of the above-mentioned nonionic detergent 1 g / 1 calc. soda 5 ml / l hydrogen peroxide (35%) 1 g / 1 tetrasodium pyrophosphate decahydrate
• Experiment 6 E: 1% of the above-mentioned nonionic detergent 1 g / 1 calc. Soda 1 ml / 1 hydrogen peroxide (35%) 0.2 g / l tetrasodium pyrophosphate decahydrate

Felt-free equipment as described in experiment 1A, but with 2% settings a and b.

Staining in the same bath as described in experiment 1A.

Example 7 Trial 7 A:

250 g of raw white knitted parts made of Shetland wool yarn of the type used in Example 1 are subjected to a whale wash as described in Example 1A and rinsed twice.

In contrast to Example 1A, the goods are not subsequently finished in a felt-free manner, but are dyed in the manner mentioned in Example 1A with the auxiliaries and dyes mentioned there. To the bath, which contained no magnesium chloride hexahydrate from a previous felt-free finishing step, 2 g / 1 Duisburg sodium sulfate was added.

Nach der Vernetzung der Produkte während 30 Minuten bei 60°C wird durch Zusatz von 3 % Essigsäure (60 %ig) der pH-Wert des Bades zur Absäuerung der Ware auf 4,5-5,0 erniedrigt und 10 Minuten lang ohne zusätzliche Energiezufuhr behandelt. Anschließend wird das Bad teilweise abgelassen, durch Zugabe von kaltem Wasser auf etwa 30°C abgekühlt, dann das Bad ganz abgelassen, die Strickteile entnommen, abgeschleudert und wie üblich getrocknet und kurz gedämpft.After the dyeing was completed, the felt-free finish was carried out from a fresh bath in the manner described in Example 1A, but with

After the products have been crosslinked for 30 minutes at 60 ° C., 3% acetic acid (60%) is added to reduce the pH of the bath to 4.5-5.0 for acidification of the goods and for 10 minutes without additional energy treated. The bath is then partially drained, cooled to about 30 ° C. by adding cold water, then the bath is drained completely, the knitted parts are removed, spun and dried as usual and briefly steamed.

Experiment 7 B:

As for experiment 7 A, but the alkaline wash liquor, as in experiment 1 E, contained 7.5 g of calc in addition to 2% of the nonionic detergent from experiment 1 A. Soda, 200 ml 35% hydrogen peroxide and 50 g tetrasodium pyrophosphate.

After 6 hours of testing in a Cubex washing machine under the type described in Example 1A, the following surface felt shrinkage values were determined in%:

Example 8 Trial 8 A

250 g of raw white knitted parts made of Shetland wool yarn of the type used in Example 1 are subjected to a whale wash as described in Experiment 1A and rinsed twice.

• In 9,5 Liter Wasser von 50°C werden 40 g Magnesiumchlorid-Hexahydrat (technisch), gelöst in etwa 250 ml Wasser von 50°C, zugegeben. Anschließend erfolgt die Zugabe von 1,5 % = 3,75 g eines nichtionogenen Egalisiermittels, gelöst in etwa 20 ml warmen Wasser. Nach kurzem Vorlauf (etwa 5 Minuten) wird die in Beispiel 1 beschriebene Farbstoffkombination hinzugefügt.

The felt-free finishing and dyeing from a fresh bath is then carried out as follows:

• 40 g of magnesium chloride hexahydrate (technical), dissolved in about 250 ml of water at 50 ° C., are added to 9.5 liters of water at 50 ° C. Then add 1.5% = 3.75 g of a nonionic leveling agent, dissolved in about 20 ml of warm water. After a short lead (about 5 minutes), the dye combination described in Example 1 is added.

Then 7.5% = 18.75 g of the setting d (= 40% aqueous solution of a thiosulfate group-containing polyether according to GB-PS 1 423 342, Example 5), dissolved in about 10 times the amount of cold soft water, are dissolved within 10 minutes slowly admitted.

The pH of the treatment bath is adjusted to about 7. The bath is heated to 60 ° C. (1 ° C./minute) within 10 minutes and then kept at this temperature for 30 minutes. The mixture is then heated to cooking temperature at 1 ° C./minute and colored and aftertreated as described in Example 1.

Trial 8 B

Like experiment 8 A, but the whale wash is carried out as described in experiment 1 E.

The surface felt shrinkage after 3 hours of testing in a Cubex washing machine using the methods described in Example 1 is:

Example 9 Trial 9 A

Material and pretreatment (whale wash) as in test 1A.

The felt-free finishing and dyeing is done from a fresh bath.

To do this, the material is first treated in 10 liters of soft water at 20 ° C for 10 minutes at a pH of 8.

Then the mixture of 3% = 7.5 g of the setting e (= about 50% solution of polytetrahydrofuran-2000-bis- (β) -aziridino-propionic acid ester according to DE-PS 2 334 655, Examples 1 and 2, product) B in isopropanol) 3% = 7.5 g of 5% sulfuric acid and 0.3% = 0.75 g of a nonionic emulsifier and treated for 45 minutes at a pH of the liquor of 6.

For dyeing, the pH of the bath is then adjusted to 5.0 with acetic acid and 1.5% = 3.75 g of a nonionic leveling agent, dissolved in 20 ml of warm water, is added. The bath is heated to 30 ° C. (1 ° C./min.) Within 10 minutes and then the dye combination described in Example 1 is added.

The mixture is then heated further to the boiling temperature (1 ° C./minute) and dyed and post-treated for 2 hours as described in Example 1.

Trial 9 B

Like experiment 9 A, but the whale wash is carried out as described in experiment 1 E.

The surface felt shrinkage after 3 hours of testing in a Cubex washing machine using the methods mentioned in Example 1 is:

Example 10 Trial 10 A

2.5 kg of raw white wool knitting yarn Nm 36/2 X4 are on a strand yarn dyeing machine in 70 liters of soft water, the 50 g (2%) of the nonionic detergent described in Example 1 and 35 g of calc. Contain soda (pH about 10) washed at 45 - 50 ° C for 15 minutes.

The liquor is drained and the yarn is rinsed twice.

The felt-free finish is then carried out from a fresh bath in the following way:

560 g of magnesium chloride hexahydrate (technical), dissolved in about 3 liters of warm water, are first added to the treatment liquor.

Then the addition of 1.5%, based on the weight of the wool yarn, of the settings a and b described in Example 1 is carried out in the manner described in Example 1. The pH of the bath is now 7.7. The cloudy equipment liquor is heated to 60 ° C (1 ° C / minute) within 30 minutes. When this temperature is reached, the fleet is almost water-clear.

By adding 35 g calc. Soda, the pH of the liquor is increased to 8.5 and the treatment is continued at 60 ° C for 30 minutes.

The liquor is then cooled to about 30 ° C. by adding cold water (overflow) and the pH is lowered to 4.5-5 by adding 1% acetic acid (60%). After a further 5 minutes, the liquor is drained off, the yarn is removed, spun off and dried.

Verusch 10 B

Like experiment 10 A, but in addition to the nonionic detergent, the wash liquor contains 50 g calc. Soda, 350 g tetrasodium pyrophosphate decahydrate and 1400 ml 35% hydrogen peroxide.

To determine the felt-free behavior, 50 cm long yarn strands (approx. 30 g) are treated according to the IWS test method 220 for 60 and 120 minutes in the Cubex washing machine.

The test showed the following length shrinkage:

Example 11 Trial 11 A

Wool yarn, laundry and felt-free finishing as in experiment 10 A. After finishing the felt-free finishing, that is to say after the treatment at 60 ° C. and pH 8.5 for 30 minutes, the yarn is not cooled, but rather as described in Example 1 in the same bath without further notice Salt additive colored with the reactive dye combination listed in Example 1.

The dyed yarn is removed, spun off and dried.

Trial 11 B

• Die Bestimmung des Filzfreiverhaltens erfolgt nach der in Beispiel 10 erwähnten Methode:
  

Like experiment 11 A, but the wash liquor contains the additives mentioned in experiment 10 B:

• The felt-free behavior is determined using the method mentioned in Example 10:
  

Example 12 Trial 12 A

2.5 kg of wool yarn of the type described in Example 10 are washed as indicated in experiment 10 A and rinsed twice.

Then the yarn from the fresh bath is dyed in the usual manner with the reactive dyes listed in Example 1.

After dyeing, a fresh bath is used as described in experiment 10 A, but with 3% of settings a and b (example 1), provided with a felt-free finish.

Trial 12 B

Like experiment 12 A, but the wash liquor contains the additives mentioned in experiment 10 B.

Felt shrinkage was determined by the method mentioned in Example 10:

Part of the yarn from both trials was knitted on a circular knitting machine to form a knitted tube 16 cm in circumference. The longitudinal shrinkage was determined on a 25 cm long, not cut section according to the IWS test methods 9 and 185 mentioned in Example 1:

Example 13 Trial 13 A

500 g of raw white wool comb (fiber fineness A / B) are in the packing insert of a cheese package in 8 liters of soft water, the 5 g (1%) of the nonionic detergent mentioned in Example 1 and 4 g of calc. Contain soda (pH about 9.5) washed for 15 minutes at 45 - 50 ° C. The liquor is drained off, the material is rinsed twice, then removed, spun off and dried.

For the felt-free finish, the wool comb is immersed in a fleet of 40 g / 1 of that in Example 1 led settings a and b and 6 g / 1 sodium hydrogen carbonate contains. The mixture is then squeezed to a wet weight gain of 80% and dried in a laboratory drying cabinet at 140 ° C. for 30 minutes.

Trial 13 B

Like experiment 13 A, but in addition to the non-ionic detergent and the calc. Soda 40 g of tetrasodium pyrophosphate decahydrate and 160 ml of 35% hydrogen peroxide.

The felt-free behavior is determined according to the _I WS test method 220 for 15 and 30 minutes in the Cubex washing machine.

The following longitudinal shrinkage values were determined:

Example 14 Trial 14 A

500 g of a raw white fabric of 120 g / m ² made from SIRO-spun wool yarn (Nm 80/2) in cloth binding are washed in 10 liters of soft water in a laboratory washing machine 10 g (2%) of the nonionic detergent described in Example 1 and 5 g calc. Contain soda (pH about 10) washed for 20 minutes at 45 - 50 ° C. The liquor is drained, rinsed twice, the goods removed, dewatered, dried and steamed.

The felt-free finish is made from a short fleet using the padding process. For this purpose, the fabric is immersed in a liquor, each containing 10 g / 1 of the settings a and b listed in Example 1 and 2 g / 1 of sodium hydrogen carbonate. It is then squeezed to a wet weight gain of 80%, the fabric is dried at 140 ° C. and then steamed for 2 minutes.

Trial 14 B

Like experiment 14 A, but in addition to the nonionic detergent and soda, the washing liquor also contains 50 g of tetrasodium pyrophosphate decahydrate and 200 ml of 35% hydrogen peroxide.

nach 6 Stunden Prüfzeit bei

The surface felt shrinkage after 3 hours of testing in a Cubex washing machine using the methods mentioned in Example 1 is:

after 6 hours of testing

Example 15 Trial 15 A

Material, pretreatment and felt-free finish as in experiment ₁ 4 _A , but a flotce is used for the felt-free finish, each containing 15 g / 1 of settings a and b and 3 g / l sodium hydrogen carbonate.

After the felt-free finish, the fabric is dyed in the usual way with the reactive dyes listed in Example 1.

Trial 15 B

Material and pre-treatment like experiment 14 B, felt-free equipment and coloring like experiment 15 A.

The surface felt shrinkage after 3 hours of testing in a Cubex washing machine according to the methcades mentioned in Example 1 is at

Example 16 Trial 16 A

Material and pretreatment like experiment 14 A

• 60 g der in Beispiel 9 erwähnten Einstellung e werden in 60 g 5 %ige Schwefelsäure eingemischt. Sofort anschließend wird dieser Ansatz mit verdünntem Ammoniak neutralisiert. Dann werden 10 g gelöstes Natriumdisulfit zugesetzt und mit Wasser auf 1 Liter aufgefüllt.

For the felt-free finishing, the fabric is immersed in a fleet that was created as follows:

• 60 g of the setting e mentioned in Example 9 are mixed into 60 g of 5% sulfuric acid. This approach is then immediately neutralized with dilute ammonia. Then 10 g of dissolved sodium disulfite are added and made up to 1 liter with water.

After dipping, the tissue is squeezed to a wet weight gain of 80%, dried at 140 ° C. and then steamed for 2 minutes.

Verusch 16 B

As for 16 A, but the washing is carried out as described in experiment 14 B.

The surface felt shrinkage after a test period of 3 hours in a Cubex washing machine using the methods mentioned in Example 1 is:

Example 17 Trial 17 A

Material, pretreatment and felt-free finish as in test 16 A.

Following the felt-free finish, the fabric is dyed in the usual way with the reactive dyes listed in Example 1.

Trial 17 B

Like 17 A, but the pretreatment (washing) is carried out as described in experiment 14 B.

The surface felt shrinkage after 1 hour of testing in a Cubex washing machine using the methods mentioned in Example 1 is:

Example 18 Trial 18 A.

Goods, pretreatment as in test 14 A. The fabric is then dyed in the usual manner using the reactive dyes listed in Example 1.

The felt-free finish was then carried out as described in Example 16.

Trial 18 B

Goods, dyeing and felt-free finish like experiment 18 A

Pretreatment (washing) like experiment 14 B.

nach 6 Stunden Prüfdauer bei

The surface felt shrinkage after 3 hours of testing in a Cubex washing machine using the methods mentioned in Example 1 is:

after 6 hours of testing

Claims (10)

1. A process for the production of felt-free finished wool by pretreating raw white wool and subsequent treatment with curable polymers and optionally dyeing, characterized in that a pretreatment liquor is used which contains an oxidizing agent. 2. The method according to claim 1, characterized in that hydrogen peroxide is added as the oxidizing agent. 3. The method according to claim 1 and 2, characterized in that the concentration of 35% aqueous hydrogen peroxide 1-50 ml / l pretreatment liquor, preferably 10-20 ml / l. 4. The method according to claim 1 to 3, characterized in that the pretreatment liquor additionally contains 0.2-10 g / l, preferably 1-5 g / 1 tetrasodium pyrophosphate decahydrate. 5. The method according to claim 1-4, characterized in that the pH of the pretreatment liquor 8-11, preferably 9-10, the temperature of the liquor 30-60 ° C, preferably 40-50 ° C and the treatment time of the wool article in the pretreatment liquor is 5-60 minutes, preferably 10-20 minutes. 6. The method according to claim 1, characterized in that a wool article pretreated according to claims 1-5 from a long liquor after the exhaust process in the presence of magnesium chloride hexahydrate with a carbamoylsulfonate group-containing polyurethane, preferably in combination with a polyurethane dispersion, equipped and, if necessary, felt-free is colored. 7. The method according to claim 1, characterized in that a pretreated wool article according to claims 1-5 after the padding process with a carbamoylsulfonate group-containing polyurethane in combination with a plastic dispersion, preferably with a polyurethane dispersion, is equipped felt-free and optionally dyed. 8. The method according to claim 1, characterized in that a pretreated wool article according to claims 1-5 from a long liquor after the exhaust process in the presence of magnesium chloride hexahydrate is equipped with a polyether containing thiosulfate gurppen and optionally dyed. 9. The method according to claim 1, characterized in that a pretreated according to claims 1-5 wool article from a long liquor after the exhaust process with an aziridine-containing polyether is finished and optionally dyed. 10. The method according to claim 1, characterized in that a wool article pretreated according to claims 1-5 after the padding process with an aziridine-containing polyether equipped and optionally dyed.