EP0356950A2 - Process for the anti-felting treatment of textiles made of wool - Google Patents
Process for the anti-felting treatment of textiles made of wool Download PDFInfo
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- EP0356950A2 EP0356950A2 EP89115770A EP89115770A EP0356950A2 EP 0356950 A2 EP0356950 A2 EP 0356950A2 EP 89115770 A EP89115770 A EP 89115770A EP 89115770 A EP89115770 A EP 89115770A EP 0356950 A2 EP0356950 A2 EP 0356950A2
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- wool
- textile materials
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
Definitions
- Textile materials made of wool which are first treated with an oxidizing or chlorinating agent and then with a compound which contains several aziridine residues by the processes of GB-PS 1 533 343, do indeed give materials which have a high shrinkage resistance and a very soft Have a grip, but they are usually somewhat yellow than the untreated material.
- This shift in color of the wool is caused by the chlorinating pretreatment stage used here and can have a disruptive effect on white or pastel-colored goods (eg light blue). Yellowing occurs in all processes that contain a chlorinating treatment step, especially if the chlorination is carried out above pH 2 to avoid uneven treatment.
- a single bath application of chlorinating substances and potassium permanganate or a procedure such as potassium permanganate treatment and subsequent chlorination of the wool damages the wool substance and usually does not solve the yellowing problem.
- permanganate treatment is in any case ruled out because permanganate attacks the dyes.
- the present invention has for its object to provide a method for finishing felt-free of textile materials consisting of wool or containing wool together with other fibers in a mixture, in which practically no yellowing and practically no damage to the fibers occurs.
- the treated textile material should also have a soft feel.
- the wool can be in all stages of processing, e.g. as fabric, knitwear, flake, sliver or yarn.
- process step a) first involves chlorination.
- suitable chlorinating agents are gaseous chlorine, water of chlorine and a number of inorganic and organic substances which use reactive chlorine, i.e. Chlorine in the +1 oxidation state.
- hypochlorous acid and its salts especially sodium hypochlorite
- water-soluble salts of dichloroisocyanuric acid preferably sodium dichloroisocyanurate.
- the use of water-soluble salts of dichloroisocyanuric acid for the chlorination of protein-containing textile materials is known.
- the chlorination is preferably carried out in an aqueous medium. Here you work either in a long fleet or by padding.
- the fleet ratio in the long fleet is usually 1:10 to 1:50.
- Sodium hypochlorite or sodium dichloroisocyanate is preferably used as the chlorinating agent.
- concentrations of the chlorinating agents in the liquor are 0.2 to 2.0 g / l, based on the active chlorine content.
- the chlorination of the textile materials is carried out at a liquor temperature of about 5 to 35, preferably 10 to 25 ° C.
- the pH of the chlorination liquor is between 2 and 7, preferably 3 to 5.
- the duration of the chlorination depends on the rate of reaction of the chlorinating agent with the wool. Depending on the pH value and temperature of the treatment liquor, it can be between 5 and 60 minutes.
- the treatment liquor preferably contains such a concentration of chlorinating agent that the active chlorine in the treatment bath is consumed after the chlorination is complete.
- the end point of chlorination can be easily determined, for example, with the help of potassium iodide starch paper.
- the protein-containing fibers of the textile materials are chlorinated to such an extent that the active chlorine absorption, based on the wool content of the dry textile materials, is 0.2 to 2, preferably 0.5 to 1.5% by weight.
- the chlorination of the textile materials can also be carried out in the presence of a wetting agent. If the chlorination is carried out in the presence of a wetting agent, the chlorination liquor contains 0.2 to 1.0 g / l of a wetting agent or a wetting agent mixture.
- Suitable wetting agents are for example alkoxylation products of long-chain alcohols, for example C8 to C18 alcohols and the alkoxylation products of phenol and alkylphenols.
- Preferred alkoxylating agents are ethylene oxide and / or propylene oxide. For example, 5 to 60, preferably 5 to 20, moles of ethylene oxide are added per mole of alcohol or phenol.
- Propylene oxide is added to the alcohols or phenols in such an amount, usually together with ethylene oxide, that water-soluble wetting agents are still obtained.
- Other suitable wetting agents are C9- to C13-alkylphosphoric monoesters or diesters and C4- to C8-alkylphosphoric acid triesters and C8-C18 alkyl sulfonates.
- the chlorination of the wool can also be carried out continuously. In process step (a) of the process according to the invention, chlorination is preferably carried out to such an extent that the active chlorine absorption is 0.2 to 2.0, preferably 0.5 to 1.5,% by weight.
- the degree of chlorination of the wool in the process according to the invention is only about 50% of the value which is usually set in the processes of the prior art.
- the chlorinated textile materials are immediately treated with peroxide, peroxysulfate or combinations thereof in process step (b).
- the hitherto customary dechlorination with sodium disulfite is eliminated.
- the chlorination of the wool is preferably carried out in process step (a) to such an extent that the liquor contains practically no active chlorine (test with potassium iodide starch paper). A so far exhausted liquor according to process step (a) need not be drained off, but can be used directly for process step (b).
- the chlorinated wool is treated with a peroxy compound under the conditions customary in wool bleaching.
- the practically exhausted chlorination liquor according to (a) 3 to 30, preferably 5 to 15 ml of hydrogen peroxide, calculated as 35% hydrogen peroxide, added to or used as the peroxy compound H2SO5 or the alkali metal or ammonium salts of this acid, or combinations of hydrogen peroxide and persulfate or peroxysulfuric acid in any ratio.
- concentration of the water-soluble salts of Caro's acid and that of peroxysulfuric acid in the treatment liquor is 1 to 10, in particular 2 to 5% by weight, based on wool.
- Hydrogen peroxide is preferably used in process step (b).
- the pH of the liquor which is suitable for the treatment of the textile material in process step (b) is, as is customary in oxidative wool bleaching, between 5 and 9.5. If one works in the pH range from 7.0 to 9.5, temperatures of the liquor between 35 and 60, preferably between 40 and 50 ° C. are chosen for the treatment of the textile material. However, it is also possible at liquor temperatures between 10 and 35 ° C to work, but then you need longer dwell times of the textile materials in the fleet. In the case of sensitive dyeings or in the case of highly bleached material, it can be advantageous to carry out the treatment in process step (b) at the lowest possible temperatures, ie between 10 and 25 ° C. In such cases, higher peroxide concentrations are usually required in addition to longer treatment times.
- bleach activators are used in concentrations of 1 to 5 g / l liquor.
- the treatment of the textile material is usually carried out at temperatures between 60 and 80 ° C. The duration of treatment is then 10 to 60 minutes.
- Suitable bleach activators are carboxyl group-containing water-soluble compounds or carboxylic acid anhydrides, for example pentaacetyl glucose, gluconic acid, pentapropionyl glucose, tetraacetyl ethylene diamine, tetraacetyl glycoluril, carboxylic acid anhydrides such as succinic acid anhydride, benzoic acid anhydride, sodium phthalate or anhydride, p-Carboxylphenylacetat, p-Sulfonylphenylacetat, p-Kresylacetat or Phenylacetat. Carboxylic acids such as fumaric acid and glutaric acid can also be used as bleach activators.
- process step (b) After the peroxy compound has practically been used up, the treatment according to process step (b) is ended.
- the textile material is then removed from the bath, rinsed and dried.
- process step (b) is followed by treatment of the textile material with polymers. If necessary, the textile material can be rinsed before this treatment.
- process step (c) the textile material is treated in a fresh bath with a solution or a dispersion of a synthetic polymer or oligomer in a manner known per se.
- the textile material can be treated from a short liquor (liquor ratio below 1:10) from a long liquor (liquor ratio 1:10 to 100), by padding, spraying or foam application.
- the polymers contained in the aqueous liquor soak on the wool fibers.
- the textile material impregnated in this way is then dried at temperatures above 60 ° C., generally in the temperature range from 80 to 150 ° C., a reaction between the polymers and the textile material or crosslinking of the polymer occurring.
- Polymers suitable for felt-free finishing are known, for example, from GB-PS 1 533 343, US-PS 4 592 757 and US Pat U.S. Patent 2,961,247 known.
- the felt-free finishing of wool with polymers is also described in detail by A. Bereck in Manualr Desirberkalender, volume 84, pages 255 ff (1980).
- the polymers described there for felt-free finishing can be used in the process according to the invention in process step (c) as a polymer.
- the process according to the invention gives wool which has been given a felt-resistant finish, which has not yellowed and also has virtually no damage. Compared to the known methods for the non-felting of wool, only about half the amount of active chlorine is required in the method according to the invention in order to produce finishing of a comparable quality.
- process steps (a) and (b) can be carried out in a single bath.
- the percentages in the examples are percentages by weight.
- the wool material was first pretreated with a liquor which contained 1% of a commercially available emulsified phosphoric acid ester and 3% 60% acetic acid.
- the pH of the liquor was 4.5, the treatment time 10 minutes, the treatment temperature 20 ° C.
- a dicarboxylic acid mixture of succinic acid, glutaric acid and adipic acid was used as the bleach activator.
- Felt-free finishing with a polymer was also carried out in a long liquor with a liquor ratio of 1:40.
- the double ester of ⁇ -aziridinopropionic acid with polytetrahydrofuran of molecular weight 2000 described in Example 1 of British Pat. No. 1,533,343 was used as the polymer.
- the polymer was first dissolved in 5% aqueous sulfuric acid to prepare the liquor and added to the treatment bath together with 2% Na2S2O5 (sodium metabisulfite). The polymer concentration was 1%.
- the textile material was treated for 30 minutes at room temperature and dried at 110 ° C. without rinsing.
- the textile material was dechlorinated, it was carried out in the bath in which the textile material was last treated. To do this, 2% Na2S2O5 and 1% of a commercially available wetting agent (adduct of 48 moles of ethylene oxide with 1 mole of castor oil) were added to this bath. The treatment lasted 10 minutes at 30 ° C. If the chlorination was carried out with sodium hypochlorite, this treatment was carried out analogously to the chlorination with the disodium salt of isocyanuric acid with the only difference that the pH was 3 and the treatment time was about 10 minutes.
- 5% sodium sulfite and 2% sodium carbonate were added to the bath.
- the pH of the liquor was adjusted to a value in the range from 7.5 to 8.0.
- the treatment lasted 20 minutes.
- the surface shrinkage during washing was determined according to IWS test method No. 31, the degree of yellowing according to DIN 6167 and the alkali solubility according to DIN 54 281.
- Table 2 Comparative Examples No. Sequence of treatments of wool Surface shrinkage in% after laundry (s) Yellow grade DIN 6167 Alkali solubility in% I chlorinate or oxidize II dechlorination III Felt-free finishing with polymers 2) 1x 5x 1 - - - 60 70 22.0 16.2 2nd 1.9% DC 1) 2% Na2S2O5 - 40 70 21.5 3rd 1.9% DC 2% Na2S2O5 2% polymer 12 38 - 4th 3.5% DC 2% Na2S2O5 - 9 62 - 23.4 5 3.5% DC 2% Na2S2O5 2% polymer - 2nd - 3rd 24.6 (26.6) - 6 7.0% KHSO5 5% Na2SO3 - 48 65 - 29.8 7 7.0% KHSO5 5% Na2SO3 2% poly
- Comparative Examples 6 and 7 achieve a lightening of the wool, but the felt-free effect is far from satisfactory even after polymer treatment.
- the oxidative treatment causes a high degree of damage to the wool, which is recognizable by the high proportions of alkali-soluble components of the wool.
- the materials additionally treated with a polymer have a high degree of freedom from felt, with no yellowing of the goods.
- the low values of the alkali solubility show that the damage to the wool in the finishing process according to the invention is negligible.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
Zur Verbesserung der Schrumpfbeständigkeit von textilen Materialien, die aus Wolle bestehen oder Wolle zusammen mit anderen Fasern im Gemisch enthalten, sind zahlreiche Methoden bekannt. Hierüber wird in der Literatur in Übersichtsartikeln berichtet, vgl. K.R. Makinson, Fiber Science Series, Band 8, Shrinkproofing of Wool, Marcel Dekker Inc., New York und Basel 1979 und A. Bereck, Deutscher Färberkalender, Band 84, 247-285 (1980). Behandlungen der textilen Materialien mit chlorhaltigen oder chlorfreien Oxidationsmitteln haben dabei große praktische Bedeutung, einerseits als selbständige Ausrüstungsverfahren, andererseits als Vorbehandlungsstufe von kombinierten Verfahren, bei denen das aus Wolle bestehende Textilmaterial zunächst oxidiert und daran anschließend mit einem Polymerisat behandelt wird. Dabei wird eine Reihe von verschiedenen Polymeren und reaktionsfähigen oligomeren Substanzen eingesetzt. Einige darunter können auch ohne eine oxidierende Vorbehandlung verwendet werden.Numerous methods are known for improving the shrink resistance of textile materials which consist of wool or which contain wool together with other fibers. This is reported in the literature in review articles, cf. K.R. Makinson, Fiber Science Series, Volume 8, Shrinkproofing of Wool, Marcel Dekker Inc., New York and Basel 1979 and A. Bereck, Deutscher Färberkalender, Volume 84, 247-285 (1980). Treatments of the textile materials with chlorine-containing or chlorine-free oxidizing agents are of great practical importance, on the one hand as an independent finishing process, on the other hand as a pretreatment stage of combined processes in which the textile material consisting of wool is first oxidized and then treated with a polymer. A number of different polymers and reactive oligomeric substances are used. Some of them can also be used without an oxidizing pretreatment.
Alle bisher bekannten Filzfreiausrüstungsverfahren weisen jedoch Nachteile auf. Behandelt man beispielsweise ein textiles Material aus Wolle mit einem kationischen Polyamid-Epichlorhydrin-Harz auf Basis von Adipinsäure und Diethylentriamin nach dem Verfahren, das aus der GB-PS 1 074 731 und der GB-PS 1 174 822 bekannt ist, so muß man mit einer deutlichen Veränderung des färberischen Verhaltens der Wolle rechnen. Führt man dagegen die Filzfreiausrüstung nach dem Verfahren der DE-OS 23 07 563 oder der DE-AS 24 14 470 durch, bei denen als Polymer Additionsprodukte von Isocyanaten und Disulfiten verwendet werden, so tritt eine deutliche Verhärtung der Wolle auf. Textile Materialien aus Wolle, die nach den Verfahren der GB-PS 1 533 343 zunächst mit einem Oxidations- oder Chlorierungsmittel und anschließend mit einer Verbindung behandelt werden, die mehrere Aziridinreste enthält, so erhält man zwar Materialien, die eine hohe Krumpfbeständigkeit und einen ausgesprochen weichen Griff aufweisen, sie sind aber in der Regel etwas gelber als das unbehandelte Material. Diese Farbtonverschiebung der Wolle wird durch die hierbei angewandte chlorierende Vorbehandlungsstufe verursacht und kann bei weißer oder pastellfarbiger Ware (z.B. hellblau) störend wirken. Eine Vergilbung tritt bei Sämtlichen Verfahren auf, die einen chlorierenden Behandlungsschritt enthalten, insbesondere dann, wenn die Chlorierung zur Vermeidung von unegaler Behandlung oberhalb von pH 2 durchgeführt wird. Es hat daher in der Praxis nicht an Versuchen gefehlt, chlorierende Filzfreiausrüstungsmittel durch andere Oxidationsmittel, wie beispielsweise Car'osche Säure (H₂SO₅), ihre Salze (Caroat®) oder durch Kaliumpermanganat zu ersetzen. Die Anwendung dieser Mittel führt zwar in der Regel nicht zur Vergilbung der Wolle oder anderer keratinhaltiger Fasern, sondern bewirkt oft eine Erhöhung des Weißgrades der so behandelten textilen Materialien. Leider ist aber die schrumpfverringernde Wirkung dieser Mittel nicht ausreichend, um Wolle waschmaschinenfest zu machen. Die Wirkung bleibt weit unterhalb der Wirksamkeit der chlorabspaltenden Substanzen, vgl. die oben zitierte Literaturstelle K.R. Makinson, Seite 311. Die Gründe dafür sind in dieser Literaturstelle auf den Seiten 233 ff ausführlich dargelegt. Eine einbadige Anwendung von chlorierenden Substanzen und Kaliumpermanganat oder eine Verfahrensweise, wie Kaliumpermanganatbehandlung und anschließende Chlorierung der Wolle, schädigt die Wollsubstanz und löst in der Regel das Vergilbungsproblem nicht. Bei gefärbter oder weiß-bunt-gemusteter Wollware scheidet eine Permanganatbehandlung ohnehin aus, weil Permanganat die Farbstoffe angreift.However, all previously known felt-free finishing processes have disadvantages. If, for example, a textile material made of wool is treated with a cationic polyamide-epichlorohydrin resin based on adipic acid and diethylenetriamine by the process known from GB-PS 1 074 731 and GB-PS 1 174 822, then one has to use expect a significant change in the dyeing behavior of the wool. If, on the other hand, the felt-free finishing is carried out according to the process of DE-OS 23 07 563 or DE-AS 24 14 470, in which addition products of isocyanates and disulfites are used as the polymer, the wool becomes significantly hardened. Textile materials made of wool, which are first treated with an oxidizing or chlorinating agent and then with a compound which contains several aziridine residues by the processes of GB-PS 1 533 343, do indeed give materials which have a high shrinkage resistance and a very soft Have a grip, but they are usually somewhat yellow than the untreated material. This shift in color of the wool is caused by the chlorinating pretreatment stage used here and can have a disruptive effect on white or pastel-colored goods (eg light blue). Yellowing occurs in all processes that contain a chlorinating treatment step, especially if the chlorination is carried out above pH 2 to avoid uneven treatment. There has therefore been no shortage of attempts in practice to replace chlorinating felt-free finishing agents by other oxidizing agents, such as Caro's acid (H₂SO₅), their salts (Caroat®) or by potassium permanganate. The application of these funds leads to Usually not for yellowing of wool or other keratin fibers, but often causes an increase in the degree of whiteness of the textile materials treated in this way. Unfortunately, however, the shrink-reducing effect of these agents is not sufficient to make wool machine washable. The effect remains far below the effectiveness of the chlorine-releasing substances, cf. the above-cited reference KR Makinson, page 311. The reasons for this are detailed in this reference on pages 233 ff. A single bath application of chlorinating substances and potassium permanganate or a procedure such as potassium permanganate treatment and subsequent chlorination of the wool damages the wool substance and usually does not solve the yellowing problem. In the case of dyed or white-colored, mustard-treated fabrics, permanganate treatment is in any case ruled out because permanganate attacks the dyes.
Sowohl nach der Chlorierung der Wolle als auch nach einer Behandlung von Wolle mit Kaliumpermanganat ist eine reduktive Nachbehandlung, z.B. mit Natriumbisulfit, unerläßlich. In dem zuerst genannten Fall der Chlorierung müssen aggressive Chloraminreste, die sich aus Wollpeptid und Chlor bilden, zerstört werden. Im zweiten Fall wird der aus Kaliumpermanganat entstandene Braunstein zu wasserlöslichen Mangan-2-Salzen reduziert und dadurch eliminiert. Daraus folgt, daß die bisher bekannten Verfahren zur Filzfreiausrüstung mindestens zweistufig sind.After chlorination of the wool as well as treatment of wool with potassium permanganate, a reductive aftertreatment, e.g. with sodium bisulfite, indispensable. In the former case of chlorination, aggressive chloramine residues formed from wool peptide and chlorine must be destroyed. In the second case, the manganese dioxide formed from potassium permanganate is reduced to water-soluble manganese-2 salts and thereby eliminated. It follows that the previously known methods for felt-free finishing are at least two stages.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Filzfreiausrüstung von textilen Materialien, die aus Wolle bestehen oder Wolle zusammen mit anderen Fasern im Gemisch enthalten, zur Verfügung zu stellen, bei dem praktisch keine Vergilbung und praktisch keine Schädigung der Fasern auftritt. Das behandelte textile Material soll außerdem einen weichen Griff aufweisen.The present invention has for its object to provide a method for finishing felt-free of textile materials consisting of wool or containing wool together with other fibers in a mixture, in which practically no yellowing and practically no damage to the fibers occurs. The treated textile material should also have a soft feel.
Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Filzfreiausrüstung von textilen Materialien, die aus Wolle bestehen oder Wolle zusammen mit anderen Fasern im Gemisch enthalten, durch Chlorieren und Bleichen der textilen Materialien, wenn man
- (a) die textilen Materialien in wäßriger Flotte so weit chloriert, daß die Aktivchloraufnahme, bezogen auf den Gehalt an Wolle der trockenen textilen Materialien, 0,2 bis 2 Gew.% beträgt,
- (b) die chlorierten textilen Materialien dann unmittelbar mit einer Wasserstoffperoxid enthaltenden Flotte behandelt, die 3 bis 30 ml Wasserstoffperoxid, berechnet auf 35 gew.%iges Wasserstoffperoxid, pro Liter gelöst enthält oder 1 bis 10 Gew.%, bezogen auf Wolle, H₂SO₅ oder eines wasserlöslichen Alkali- oder Ammoniumsalzes der Perschwefelsäure darauf in wäßriger Lösung einwirken läßt und gegebenenfalls
- (c) 0, 5 bis 5 Gew.%, bezogen auf die textilen Materialien, eines bekannten Polymeren für die Filzfreiausrüstung aufbringt.
- (a) chlorinating the textile materials in an aqueous liquor to such an extent that the active chlorine absorption, based on the wool content of the dry textile materials, is 0.2 to 2% by weight,
- (b) the chlorinated textile materials are then treated directly with a liquor containing hydrogen peroxide, which contains 3 to 30 ml of hydrogen peroxide, calculated on 35% by weight hydrogen peroxide, per liter dissolved or 1 to 10% by weight, based on wool, H₂SO₅ or a water-soluble alkali or ammonium salt of persulfuric acid can act on it in aqueous solution and optionally
- (c) 0.5 to 5% by weight, based on the textile materials, of a known polymer for the felt-free finishing.
Die Wolle kann in allen Verarbeitungsstufen vorliegen, z.B. als Gewebe, Maschenware, Flocke, Kammzug oder Garn.The wool can be in all stages of processing, e.g. as fabric, knitwear, flake, sliver or yarn.
Zur Filzfreiausrüstung des Wollmaterials erfolgt in der Verfahrensstufe a) zunächst eine Chlorierung. Als chlorierende Agenzien kommen beispielsweise gasförmiges Chlor, Chlorwasser und eine Reihe von anorganischen und organischen Substanzen in Betracht, die reaktives Chlor, d.h. Chlor in der Oxidationsstufe +1, enthalten. Von besonderer technischer Bedeutung sind dabei hypochlorige Säure und ihre Salze, insbesondere Natriumhypochlorit sowie wasserlösliche Salze der Dichlorisocyanursäure, vorzugsweise Natriumdichlorisocyanurat. Die Verwendung von wasserlöslichen Salzen der Dichlorisocyanursäure zur Chlorierung von proteinhaltigen textilen Materialien ist bekannt. Die Chlorierung wird vorzugsweise in einem wäßrigen Medium durchgeführt. Hierbei arbeitet man entweder in langer Flotte oder durch Foulardieren. Das Flottenverhältnis in der langen Flotte beträgt in der Regel 1:10 bis 1:50. Vorzugsweise verwendet man als chlorierendes Agens Natriumhypochlorit oder Natriumdichlorisocyanat. Die Konzentrationen der chlorierenden Agenzien in der Flotte betragen 0,2 bis 2,0 g/l, bezogen auf den Aktivchlorgehalt. Die Chlorierung der textilen Materialien wird bei einer Flottentemperatur von etwa 5 bis 35, vorzugsweise 10 bis 25°C durchgeführt. Der pH-Wert der Chlorierungsflotte liegt zwischen 2 und 7, vorzugsweise 3 bis 5. Die Dauer der Chlorierung richtet sich nach der Reaktionsgeschwindigkeit des Chlorierungsmittels mit den Wolle. Sie kann je nach pH-Wert und Temperatur der Behandlungsflotte zwischen 5 und 60 Minuten betragen. Die Behandlungsflotte enthält vorzugsweise eine solche Konzentration an Chlorierungsmittel, daß nach Abschluß der Chlorierung das aktive Chlor im Behandlungsbad verbraucht ist. Der Endpunkt der Chlorierung kann beispielsweise mit Hilfe von Kaliumjodid-Stärke-Papier leicht festgestellt werden. Die proteinhaltigen Fasern der textilen Materialien werden soweit chloriert, daß die Aktivchloraufnahme, bezogen auf den Wollgehalt der trockenen textilen Materialien, 0,2 bis 2, vorzugsweise 0,5 bis 1,5 Gew.% beträgt.In order to provide the wool material with a felt-free finish, process step a) first involves chlorination. Examples of suitable chlorinating agents are gaseous chlorine, water of chlorine and a number of inorganic and organic substances which use reactive chlorine, i.e. Chlorine in the +1 oxidation state. Of particular technical importance are hypochlorous acid and its salts, especially sodium hypochlorite, and water-soluble salts of dichloroisocyanuric acid, preferably sodium dichloroisocyanurate. The use of water-soluble salts of dichloroisocyanuric acid for the chlorination of protein-containing textile materials is known. The chlorination is preferably carried out in an aqueous medium. Here you work either in a long fleet or by padding. The fleet ratio in the long fleet is usually 1:10 to 1:50. Sodium hypochlorite or sodium dichloroisocyanate is preferably used as the chlorinating agent. The concentrations of the chlorinating agents in the liquor are 0.2 to 2.0 g / l, based on the active chlorine content. The chlorination of the textile materials is carried out at a liquor temperature of about 5 to 35, preferably 10 to 25 ° C. The pH of the chlorination liquor is between 2 and 7, preferably 3 to 5. The duration of the chlorination depends on the rate of reaction of the chlorinating agent with the wool. Depending on the pH value and temperature of the treatment liquor, it can be between 5 and 60 minutes. The treatment liquor preferably contains such a concentration of chlorinating agent that the active chlorine in the treatment bath is consumed after the chlorination is complete. The end point of chlorination can be easily determined, for example, with the help of potassium iodide starch paper. The protein-containing fibers of the textile materials are chlorinated to such an extent that the active chlorine absorption, based on the wool content of the dry textile materials, is 0.2 to 2, preferably 0.5 to 1.5% by weight.
Die Chlorierung der textilen Materialien kann auch in Gegenwart eines Netzmittels durchgeführt werden. Sofern die Chlorierung in Gegenwart eines Netzmittels erfolgt, enthält die Chlorierungsflotte 0,2 bis 1,0 g/l eines Netzmittels oder eines Netzmittelgemisches. Geeignete Netzmittel sind beispielsweise Alkoxylierungsprodukte von langkettigen Alkoholen, z.B. C₈- bis C₁₈-Alkoholen sowie die Alkoxylierungsprodukte von Phenol und Alkylphenolen. Als Alkoxylierungsmittel kommen vorzugsweise Ethylenoxid und/oder Propylenoxid in Betracht. Pro Mol Alkohol oder Phenol lagert man beispielsweise 5 bis 60, vorzugsweise 5 bis 20 Mol Ethylenoxid an. Propylenoxid wird in einer solchen Menge, meistens zusammen mit Ethylenoxid an die Alkohole oder Phenole angelagert, daß man noch wasserlösliche Netzmittel erhält. Weitere geeignete Netzmittel sind C₉- bis C₁₃-Alkylphosphorsäuremono- oder -diester sowie C₄- bis C₈-Alkylphosphorsäuretriester und C₈-C₁₈-Alkylsulfonate. Die Chlorierung der Wolle kann auch kontinuierlich durchgeführt werden. In der Verfahrensstufe (a) des erfindungsgemäßen Verfahrens wird vorzugsweise soweit chloriert, daß die Aktivchloraufnahme 0,2 bis 2,0, vorzugsweise 0,5 bis 1,5 Gew.% beträgt. Der Chlorierungsgrad der Wolle beträgt bei dem erfindungsgemäßen Verfahren etwa nur 50 % des Wertes, der bei den Verfahren des Standes der Technik üblicherweise eingestellt wird.The chlorination of the textile materials can also be carried out in the presence of a wetting agent. If the chlorination is carried out in the presence of a wetting agent, the chlorination liquor contains 0.2 to 1.0 g / l of a wetting agent or a wetting agent mixture. Suitable wetting agents are for example alkoxylation products of long-chain alcohols, for example C₈ to C₁₈ alcohols and the alkoxylation products of phenol and alkylphenols. Preferred alkoxylating agents are ethylene oxide and / or propylene oxide. For example, 5 to 60, preferably 5 to 20, moles of ethylene oxide are added per mole of alcohol or phenol. Propylene oxide is added to the alcohols or phenols in such an amount, usually together with ethylene oxide, that water-soluble wetting agents are still obtained. Other suitable wetting agents are C₉- to C₁₃-alkylphosphoric monoesters or diesters and C₄- to C₈-alkylphosphoric acid triesters and C₈-C₁₈ alkyl sulfonates. The chlorination of the wool can also be carried out continuously. In process step (a) of the process according to the invention, chlorination is preferably carried out to such an extent that the active chlorine absorption is 0.2 to 2.0, preferably 0.5 to 1.5,% by weight. The degree of chlorination of the wool in the process according to the invention is only about 50% of the value which is usually set in the processes of the prior art.
Nach Beendigung der Chlorierung erfolgt unmittelbar eine Behandlung der chlorierten textilen Materialien mit Peroxid, Peroxysulfat oder Kombinationen derselben im Verfahrensschritt (b). Beim erfindungsgemäßen Verfahren entfällt das bisher übliche Entchloren mit Natriumdisulfit. Die Chlorierung der Wolle wird vorzugsweise im Verfahrensschritt (a) soweit durchgeführt, daß die Flotte praktisch kein aktives Chlor mehr enthält (Prüfung mit Kaliumjodid-Stärke-Papier). Eine so weit erschöpfte Flotte gemäß Verfahrensschritt (a) braucht nicht abgelassen zu werden, sondern kann direkt für den Verfahrensschritt (b) verwendet werden. Im Verfahrensschritt (b) erfolgt die Behandlung der chlorierten Wolle mit einer Peroxiverbindung unter den bei der Wollbleiche üblichen Bedingungen. Zu diesem Zweck setzt man der praktisch erschöpften Chlorierungsflotte gemäß (a) 3 bis 30, vorzugsweise 5 bis 15 ml Wasserstoffperoxid, berechnet als 35 %iges Wasserstoffperoxid, zu oder verwendet als Peroxiverbindung H₂SO₅ oder die Alkali- oder Ammoniumsalze dieser Säure, oder Kombinationen von Wasserstoffperoxid und Persulfat oder Peroxyschwefelsäure in jedem beliebigen Verhältnis. Die Konzentration der wasserlöslichen Salze der Caro'schen Säure sowie die der Peroxyschwefelsäure in der Behandlungsflotte liegt bei 1 bis 10, insbesondere 2 bis 5 Gew.%, bezogen auf Wolle. Vorzugsweise verwendet man im Verfahrensschritt (b) Wasserstoffperoxid.After the chlorination has ended, the chlorinated textile materials are immediately treated with peroxide, peroxysulfate or combinations thereof in process step (b). In the process according to the invention, the hitherto customary dechlorination with sodium disulfite is eliminated. The chlorination of the wool is preferably carried out in process step (a) to such an extent that the liquor contains practically no active chlorine (test with potassium iodide starch paper). A so far exhausted liquor according to process step (a) need not be drained off, but can be used directly for process step (b). In process step (b) the chlorinated wool is treated with a peroxy compound under the conditions customary in wool bleaching. For this purpose, the practically exhausted chlorination liquor according to (a) 3 to 30, preferably 5 to 15 ml of hydrogen peroxide, calculated as 35% hydrogen peroxide, added to or used as the peroxy compound H₂SO₅ or the alkali metal or ammonium salts of this acid, or combinations of hydrogen peroxide and persulfate or peroxysulfuric acid in any ratio. The concentration of the water-soluble salts of Caro's acid and that of peroxysulfuric acid in the treatment liquor is 1 to 10, in particular 2 to 5% by weight, based on wool. Hydrogen peroxide is preferably used in process step (b).
Der pH-Wert der Flotte, die für die Behandlung des textilen Materials im Verfahrensschritt (b) in Betracht kommt, liegt wie bei der oxidativen Wollbleiche üblich, zwischen 5 und 9,5. Wenn man in dem pH-Bereich von 7,0 bis 9,5 arbeitet, wählt man für die Behandlung des textilen Materials Temperaturen der Flotte zwischen 35 und 60, vorzugsweise zwischen 40 und 50°C. Es ist jedoch auch möglich, bei Flottentemperaturen zwischen 10 und 35°C zu arbeiten, jedoch benötigt man dann längere Verweilzeiten der textilen Materialien in der Flotte. Bei empfindlichen Färbungen oder bei stark gebleichtem Material kann es vorteilhaft sein, die Behandlung im Verfahrensschritt (b) bei möglichst tiefen Temperaturen, d.h. zwischen 10 und 25°C durchzuführen. In solchen Fällen benötigt man in aller Regel außer längeren Behandlungszeiten auch höhere Peroxidkonzentrationen. Bei der Arbeitsweise im schwach sauren pH-Bereich, z.B. von 5 bis 7, ist es oft vorteilhaft, die Behandlung des textilen Materials im Verfahrensschritt (b) in Gegenwart eines Bleichaktivators durchzuführen. Bleichaktivatoren werden dabei in Konzentrationen von 1 bis 5 g/l Flotte verwendet. Beim Arbeiten im sauren pH-Bereich und der gegebenenfalls in Betracht kommenden Mitverwendung von Bleichaktivatoren führt man die Behandlung des textilen Materials in der Regel bei Temperaturen zwischen 60 und 80°C durch. Die Behandlungsdauer berägt dann 10 bis 60 Minuten. Geeignete Bleichaktivatoren sind Carboxylgruppen aufweisende wasserlösliche Verbindungen oder Carbonsäureanhydride, z.B. Pentaacetylglukose, Glukonsäure, Pentapropionylglukose, Tetraacetylethylendiamin, Tetraacetylglykoluril, Carbonsäureanhydride, wie Bernsteinsäureanhydrid, Benzoesäureanhydrid oder Phthalsäureanhydrid, Natrium- oder Magnesiumdiacetylphosphat sowie Verbindungen, die unter Anwendungsbedingungen unter Bildung von Carbonsäure hydrolysieren, z.B. Phenolester, wie p-Carboxylphenylacetat, p-Sulfonylphenylacetat, p-Kresylacetat oder Phenylacetat. Auch Carbonsäuren, wie Fumarsäure und Glutarsäure können als Bleichaktivator verwendet werden.The pH of the liquor which is suitable for the treatment of the textile material in process step (b) is, as is customary in oxidative wool bleaching, between 5 and 9.5. If one works in the pH range from 7.0 to 9.5, temperatures of the liquor between 35 and 60, preferably between 40 and 50 ° C. are chosen for the treatment of the textile material. However, it is also possible at liquor temperatures between 10 and 35 ° C to work, but then you need longer dwell times of the textile materials in the fleet. In the case of sensitive dyeings or in the case of highly bleached material, it can be advantageous to carry out the treatment in process step (b) at the lowest possible temperatures, ie between 10 and 25 ° C. In such cases, higher peroxide concentrations are usually required in addition to longer treatment times. When working in the weakly acidic pH range, for example from 5 to 7, it is often advantageous to carry out the treatment of the textile material in process step (b) in the presence of a bleach activator. Bleach activators are used in concentrations of 1 to 5 g / l liquor. When working in the acidic pH range and the possible use of bleach activators, the treatment of the textile material is usually carried out at temperatures between 60 and 80 ° C. The duration of treatment is then 10 to 60 minutes. Suitable bleach activators are carboxyl group-containing water-soluble compounds or carboxylic acid anhydrides, for example pentaacetyl glucose, gluconic acid, pentapropionyl glucose, tetraacetyl ethylene diamine, tetraacetyl glycoluril, carboxylic acid anhydrides such as succinic acid anhydride, benzoic acid anhydride, sodium phthalate or anhydride, p-Carboxylphenylacetat, p-Sulfonylphenylacetat, p-Kresylacetat or Phenylacetat. Carboxylic acids such as fumaric acid and glutaric acid can also be used as bleach activators.
Nachdem die Peroxiverbindung praktisch verbraucht ist, ist die Behandlung gemäß Verfahrensstufe (b) beendet. Das textile Material wird dann dem Bad entnommen, gespült und getrocknet. Falls jedoch eine besonders effiziente Filzfreiausrüstung von textilen Materialien erwünscht ist, schließt sich an den Verfahrensschritt (b) eine Behandlung des textilen Materials mit Polymeren an. Gegebenenfalls kann vor dieser Behandlung ein Spülen des textilen Materials erfolgen. Im Verfahrensschritt (c) wird das Textilgut in einem frischen Bad mit einer Lösung oder einer Dispersion eines synthetischen Polymeren bzw. Oligomeren in an sich bekannter Weise behandelt. Die Behandlung des textilen Materials kann dabei sowohl aus kurzer Flotte (Flottenverhältnis von unter 1:10) aus langer Flotte (Flottenverhältnis 1:10 bis 100), durch Klotzen, Sprühen oder Schaumauftrag erfolgen. Die in der wäßrigen Flotte enthaltenen Polymeren ziehen dabei auf die Wollfasern auf. Das so imprägnierte Textilgut wird anschließend bei Temperaturen oberhalb von 60°C, in der Regel in dem Temperaturbereich von 80 bis 150°C getrocknet, wobei eine Reaktion zwischen den Polymeren und dem Textilmaterial bzw. eine Vernetzung des Polymeren eintritt. Für die Filzfreiausrüstung geeignete Polymere sind beispielsweise aus der GB-PS 1 533 343, der US-PS 4 592 757 und der US-PS 2 961 247 bekannt. Die Filzfreiausrüstung von Wolle mit Polymeren wird außerdem von A. Bereck in Deutscher Färberkalender, Band 84, Seiten 255 ff (1980) ausführlich beschrieben. Die dort zur Filzfreiausrüstung beschriebenen Polymeren können bei dem erfindungsgemäßen Verfahren in der Verfahrensstufe (c) als Polymer eingesetzt werden. Nach dem erfindungsgemäßen Verfahren erhält man filzfest ausgerüstete Wolle, die nicht vergilbt ist und auch praktisch keine Schädigung aufweist. Verglichen mit den bekannten Verfahren zur Filzfreiausrüstung von Wolle benötigt man bei dem erfindungsgemäßen Verfahren nur etwa die Hälfte der Menge an Aktivchlor, um Ausrüstungen einer vergleichbaren Qualität herzustellen. Im Unterschied zum Stand der Technik können die Verfahrensstufen (a) und (b) in einem einzigen Bad durchgeführt werden.After the peroxy compound has practically been used up, the treatment according to process step (b) is ended. The textile material is then removed from the bath, rinsed and dried. However, if particularly efficient felt-free finishing of textile materials is desired, process step (b) is followed by treatment of the textile material with polymers. If necessary, the textile material can be rinsed before this treatment. In process step (c), the textile material is treated in a fresh bath with a solution or a dispersion of a synthetic polymer or oligomer in a manner known per se. The textile material can be treated from a short liquor (liquor ratio below 1:10) from a long liquor (liquor ratio 1:10 to 100), by padding, spraying or foam application. The polymers contained in the aqueous liquor soak on the wool fibers. The textile material impregnated in this way is then dried at temperatures above 60 ° C., generally in the temperature range from 80 to 150 ° C., a reaction between the polymers and the textile material or crosslinking of the polymer occurring. Polymers suitable for felt-free finishing are known, for example, from GB-PS 1 533 343, US-PS 4 592 757 and US Pat U.S. Patent 2,961,247 known. The felt-free finishing of wool with polymers is also described in detail by A. Bereck in Deutscher Färberkalender, volume 84, pages 255 ff (1980). The polymers described there for felt-free finishing can be used in the process according to the invention in process step (c) as a polymer. The process according to the invention gives wool which has been given a felt-resistant finish, which has not yellowed and also has virtually no damage. Compared to the known methods for the non-felting of wool, only about half the amount of active chlorine is required in the method according to the invention in order to produce finishing of a comparable quality. In contrast to the prior art, process steps (a) and (b) can be carried out in a single bath.
Die Prozentangaben in den Beispielen sind Gewichtsprozent.The percentages in the examples are percentages by weight.
Für sämtliche Beispiele und Vergleichsbeispiele wurde ein Wollgestrick verwendet, das extrem stark zum Filzschrumpfen neigte. Alle Behandlungen erfolgten in langer Flotte bei einem Flottenverhältnis von 1:40. Die im folgenden angegebenen Anwendungsmengen von Hilfsmitteln sind stets in Gewichtsprozent, bezogen auf das Wollgewicht, berechnet. Die Versuchsbedingungen und Ergebnisse sind in den Tabellen 1 und 2 zusammengefaßt. Im folgenden werden für die einzelnen Behandlungen die Bedingungen angegeben, unter denen die Behandlung jeweils erfolgt ist.For all examples and comparative examples, a woolen knit was used, which tended to shrink felt extremely. All treatments were carried out in a long liquor with a liquor ratio of 1:40. The application quantities of auxiliaries indicated below are always calculated in percent by weight, based on the weight of the wool. The test conditions and results are summarized in Tables 1 and 2. The conditions under which the treatment was carried out are given below for the individual treatments.
Das Wollmaterial wurde zunächst mit einer Flotte vorbehandelt, die 1 % eines handelsüblichen emulgierten Phosphorsäureesters und 3 % 60 %ige Essigsäure enthielt. Der pH-Wert der Flotte betrug 4,5, die Behandlungsdauer 10 Minuten, die Behandlungstemperatur 20°C.The wool material was first pretreated with a liquor which contained 1% of a commercially available emulsified phosphoric acid ester and 3% 60% acetic acid. The pH of the liquor was 4.5, the treatment time 10 minutes, the treatment temperature 20 ° C.
Nach dieser Behandlung setzte man jeweils zu diesem Bad die in den Tabellen angegebene Menge an Chlorbleichlauge oder Natriumdichlorisocyanurat zu. Das Textilmaterial wurde in dieser Flotte 30 bis 45 Minuten behandelt, d.h. bis Kaliumjodid-Stärke-Indikatorpapier sich nicht mehr blau färbte. Die Behandlungstemperatur betrug 20°C, der pH-Wert der Flotte lag bei 4 bis 4,5.After this treatment, the amount of chlorine bleach or sodium dichloroisocyanurate given in the tables was added to this bath. The textile material was treated in this liquor for 30 to 45 minutes, ie until potassium iodide starch indicator paper no longer turned blue. The treatment temperature was 20 ° C, the pH of the liquor was 4 to 4.5.
Die in der Tabelle 1 angegebenen Mischungen aus Wasserstoffperoxid, Na₄P₂O₇ und gegebenenfalls Bleichaktivator wurden zu dem nach Abschluß der Chlorierung gemäß Verfahrensschritt (a) vorliegenden Bad direkt zugesetzt, und zwar nachdem die Prüfung auf aktives Chlor mit Kaliumjodid-Stärke-Indikator-Papier negativ ausfiel.The mixtures of hydrogen peroxide, Na₄P₂O₇ and optionally bleach activator specified in Table 1 were added directly to the bath present after completion of the chlorination according to process step (a), specifically after the test for active chlorine with potassium iodide starch indicator paper was negative.
Als Bleichaktivator wurde ein Dicarbonsäuregemisch aus Bernsteinsäure, Glutarsäure und Adipinsäure verwendet.A dicarboxylic acid mixture of succinic acid, glutaric acid and adipic acid was used as the bleach activator.
Die Filzfreiausrüstung mit einem Polymeren erfolgte ebenfalls in langer Flotte bei einem Flottenverhältnis von 1:40. Als Polymer wurde der im Beispiel 1 der GB-PS 1 533 343 beschriebene zweifache Ester der β-Aziridinopropionsäure mit Polytetrahydrofuran vom Molekulargewicht 2000 eingesetzt. Das Polymere wurde zur Bereitung der Flotte zunächst in 5 %iger wäßriger Schwefelsäure gelöst und zusammen mit 2 % Na₂S₂O₅ (Natriummetabisulfit) in das Behandlungsbad gegeben. Die Polymerkonzentration betrug 1 %. Das Textilmaterial wurde jeweils 30 Minuten lang bei Raumtemperatur behandelt und ohne Spülen bei 110°C getrocknet.Felt-free finishing with a polymer was also carried out in a long liquor with a liquor ratio of 1:40. The double ester of β-aziridinopropionic acid with polytetrahydrofuran of molecular weight 2000 described in Example 1 of British Pat. No. 1,533,343 was used as the polymer. The polymer was first dissolved in 5% aqueous sulfuric acid to prepare the liquor and added to the treatment bath together with 2% Na₂S₂O₅ (sodium metabisulfite). The polymer concentration was 1%. The textile material was treated for 30 minutes at room temperature and dried at 110 ° C. without rinsing.
Sofern eine Entchlorung des Textilmaterials durchgeführt wurde, erfolgte sie in dem Bad, in dem das Textilmaterial zuletzt behandelt wurde. Hierzu setzte man diesem Bad jeweils 2 % Na₂S₂O₅ und 1 % eines handelsüblichen Netzmittels (Anlagerungsprodukt von 48 Mol Ethylenoxid an 1 Mol Ricinusöl) zu. Die Behandlung dauerte 10 Minuten bei 30°C. Sofern die Chlorierung mit Natriumhypochlorit durchgeführt wurde, erfolgte diese Behandlung analog der Chlorierung mit dem Dinatriumsalz der Isocyanursäure mit dem einzigen Unterschied, daß der pH-Wert 3 betrug und die Behandlungsdauer ca. 10 Minuten betrug.If the textile material was dechlorinated, it was carried out in the bath in which the textile material was last treated. To do this, 2% Na₂S₂O₅ and 1% of a commercially available wetting agent (adduct of 48 moles of ethylene oxide with 1 mole of castor oil) were added to this bath. The treatment lasted 10 minutes at 30 ° C. If the chlorination was carried out with sodium hypochlorite, this treatment was carried out analogously to the chlorination with the disodium salt of isocyanuric acid with the only difference that the pH was 3 and the treatment time was about 10 minutes.
wurde so durchgeführt, daß man die Wolle zunächst mit einer Flotte vorbehandelte, die 1 % 85 %iger Ameisensäure und 1 % eines handelsüblichen emulgierten Phosphorsäureesters enthielt. Die Behandlung dauerte 5 Minuten und wurde bei 30°C und einem pH-Wert von 4 vorgenommen. Anschließend fügte man 7 % KHSO₅ innerhalb von 5 Minuten zu. Die Behandlung dauerte ca. 30 Minuten. Der Endpunkt der Behandlung war dann erreicht, sobald sich Kaliumjodid-Stärke-Papier nicht mehr beim Benetzen mit der Flotte blau färbte.was carried out in such a way that the wool was first pretreated with a liquor which contained 1% 85% formic acid and 1% of a commercially available emulsified phosphoric acid ester. The treatment lasted 5 minutes and was carried out at 30 ° C. and a pH of 4. Then 7% KHSO₅ was added within 5 minutes. The treatment lasted approx. 30 minutes. The end point of the treatment was reached as soon as potassium iodide starch paper no longer turned blue when wetted with the liquor.
Für die reduktive Nachbehandlung gab man zu dem Bad 5 % Natriumsulfit und 2 % Natriumcarbonat. Der pH-Wert der Flotte wurde auf einen Wert in dem Bereich von 7,5 bis 8,0 eingestellt. Die Behandlungsdauer betrug 20 Minuten.For the reductive aftertreatment, 5% sodium sulfite and 2% sodium carbonate were added to the bath. The pH of the liquor was adjusted to a value in the range from 7.5 to 8.0. The treatment lasted 20 minutes.
Der Flächenkrumpf beim Waschen wurde nach der IWS-Testmethode Nr. 31, der Gelbgrad nach DIN 6167 und die Alkalilöslichkeit nach DIN 54 281 bestimmt.
Wie die Ergebnisse in den Tabellen 1 und 2 zeigen, kann ein ausreichender Filzfreieffekt auf dem untersuchten Material nur mittels einer intensiven Chlorierung, vgl. Vergleichsbeispiel 5 und anschließender Behandlung mit dem Polymer erreicht werden. Diese Vorbehandlung verursacht jedoch eine deutliche Vergilbung der Wolle.As the results in Tables 1 and 2 show, a sufficient felt-free effect on the investigated material can only be achieved by intensive chlorination, cf. Comparative example 5 and subsequent treatment with the polymer can be achieved. However, this pretreatment causes the wool to become markedly yellowed.
Verwendet man anstelle eines Chlorierungsmittels KHSO₅, vgl. Vergleichsbeispiele 6 und 7, so erreicht man zwar eine Aufhellung der Wolle, jedoch ist der Filzfreieffekt auch nach einer Polymerbehandlung bei weitem nicht zufriedenstellend. Außerdem verursacht die oxidative Behandlung ein hohes Maß an Wollschädigung, die an den hohen Anteilen von in Alkali löslichen Bestandteilen der Wolle erkenntlich ist.If you use KHSO₅ instead of a chlorinating agent, cf. Comparative Examples 6 and 7 achieve a lightening of the wool, but the felt-free effect is far from satisfactory even after polymer treatment. In addition, the oxidative treatment causes a high degree of damage to the wool, which is recognizable by the high proportions of alkali-soluble components of the wool.
Gemäß den Beispielen 1 bis 10 erzielt man bei den noch zusätzlich mit einem Polymer behandelten Materialien einen hohen Grad an Filzfreiheit, wobei keine Vergilbung der Ware auftritt. Die niedrigen Werte der Alkalilöslichkeit zeigen, daß die Schädigung der Wolle bei dem erfindungsgemäßen Ausrüstungsverfahren vernachlässigbar gering ist.According to Examples 1 to 10, the materials additionally treated with a polymer have a high degree of freedom from felt, with no yellowing of the goods. The low values of the alkali solubility show that the damage to the wool in the finishing process according to the invention is negligible.
Claims (5)
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DE19883829631 DE3829631A1 (en) | 1988-09-01 | 1988-09-01 | METHOD FOR FELT-FREE FINISHING OF TEXTILE MATERIALS FROM WOOL |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1992000412A1 (en) * | 1990-06-26 | 1992-01-09 | Precision Processes (Textiles) Ltd. | A method for the treatment of wool |
US5238463A (en) * | 1990-08-27 | 1993-08-24 | Diversey Corporation | Method of treating denim fabric |
GB2264724A (en) * | 1992-02-28 | 1993-09-08 | Samuel Eden & Son Limited | A method of increasing the shrink resistance of wool |
WO1995002085A1 (en) * | 1993-07-09 | 1995-01-19 | Lanificio Zignone S.R.L. | Process for producing nonshrink woollen fabrics for clothing |
WO1999004083A1 (en) * | 1997-07-15 | 1999-01-28 | Consejo Superior De Investigaciones Cientificas | Process for confering to the wool shrinking resistance properties |
CN101519838B (en) * | 2009-03-26 | 2013-02-06 | 浙江新中和羊毛有限公司 | Wool shrinkproof mercerization method |
AT514752A1 (en) * | 2013-09-12 | 2015-03-15 | Schoeller Gmbh & Cokg | Method for chlorine-free felt-free finishing of wool |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR920008960B1 (en) * | 1990-08-24 | 1992-10-12 | 한얼앙고라모직 주식회사 | Producing method of angora-wool yarn |
Citations (3)
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DE1066985B (en) * | 1958-08-21 | 1959-10-15 | Badische Anilin- und Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein | Process for the felt and shrink-proofing of wool and textiles containing wool |
DE2326463A1 (en) * | 1973-05-24 | 1974-12-19 | Basf Ag | Antifelting and creaseproofing treatment of wool - with chlorocyanuric acid soln. and then with a polymer dispersion |
JPS57167452A (en) * | 1981-04-09 | 1982-10-15 | Toyo Boseki | Modification of animal wool fiber |
-
1988
- 1988-09-01 DE DE19883829631 patent/DE3829631A1/en not_active Withdrawn
-
1989
- 1989-08-21 JP JP1213114A patent/JPH0299663A/en active Pending
- 1989-08-26 EP EP19890115770 patent/EP0356950A3/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1066985B (en) * | 1958-08-21 | 1959-10-15 | Badische Anilin- und Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein | Process for the felt and shrink-proofing of wool and textiles containing wool |
DE2326463A1 (en) * | 1973-05-24 | 1974-12-19 | Basf Ag | Antifelting and creaseproofing treatment of wool - with chlorocyanuric acid soln. and then with a polymer dispersion |
JPS57167452A (en) * | 1981-04-09 | 1982-10-15 | Toyo Boseki | Modification of animal wool fiber |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 98, no. 12, 21 M{rz 1983 Columbus, Ohio, USA "MODIFICATION OF HAIR FIBERS" ref. no. 90996E & JP-A-57 167 452 (TOYOBO) 15-10-1982 * |
MELLIAND TEXTILBERICHTE. vol. 70, no. 6, Juni 1989, HEIDELBERG DE Seiten 452 - 454; ATTILA BERECK: "Filzfestausr}stung in langer Flotte ohne Vergilbung" * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992000412A1 (en) * | 1990-06-26 | 1992-01-09 | Precision Processes (Textiles) Ltd. | A method for the treatment of wool |
AU656527B2 (en) * | 1990-06-26 | 1995-02-09 | Coats Shelfco Precision Limited | A method for the treatment of wool |
US5697983A (en) * | 1990-06-26 | 1997-12-16 | Precision Processes Textiles | Method for the treatment of wool |
US5238463A (en) * | 1990-08-27 | 1993-08-24 | Diversey Corporation | Method of treating denim fabric |
GB2264724A (en) * | 1992-02-28 | 1993-09-08 | Samuel Eden & Son Limited | A method of increasing the shrink resistance of wool |
WO1995002085A1 (en) * | 1993-07-09 | 1995-01-19 | Lanificio Zignone S.R.L. | Process for producing nonshrink woollen fabrics for clothing |
WO1999004083A1 (en) * | 1997-07-15 | 1999-01-28 | Consejo Superior De Investigaciones Cientificas | Process for confering to the wool shrinking resistance properties |
ES2130080A1 (en) * | 1997-07-15 | 1999-06-16 | Consejo Superior Investigacion | Process for confering to the wool shrinking resistance properties |
CN101519838B (en) * | 2009-03-26 | 2013-02-06 | 浙江新中和羊毛有限公司 | Wool shrinkproof mercerization method |
AT514752A1 (en) * | 2013-09-12 | 2015-03-15 | Schoeller Gmbh & Cokg | Method for chlorine-free felt-free finishing of wool |
WO2015035439A1 (en) | 2013-09-12 | 2015-03-19 | Schoeller Gmbh & Cokg | Method for chlorine-free anti-felting treatment of wool |
US10385504B2 (en) | 2013-09-12 | 2019-08-20 | Schoeller Gmbh & Co Kg | Method for the chlorine-free anti-felting treatment of wool |
Also Published As
Publication number | Publication date |
---|---|
DE3829631A1 (en) | 1990-03-15 |
EP0356950A3 (en) | 1991-09-11 |
JPH0299663A (en) | 1990-04-11 |
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