EP0098544B1 - Process for the anti-felt treatment of keratinous fibres consisting of a basic oxidation catalyzed by a metal salt, and fibres obtained according to the process - Google Patents

Process for the anti-felt treatment of keratinous fibres consisting of a basic oxidation catalyzed by a metal salt, and fibres obtained according to the process Download PDF

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Publication number
EP0098544B1
EP0098544B1 EP83106432A EP83106432A EP0098544B1 EP 0098544 B1 EP0098544 B1 EP 0098544B1 EP 83106432 A EP83106432 A EP 83106432A EP 83106432 A EP83106432 A EP 83106432A EP 0098544 B1 EP0098544 B1 EP 0098544B1
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EP
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Prior art keywords
bath
purified water
rinsed
treated
salts
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EP83106432A
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German (de)
French (fr)
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EP0098544A2 (en
EP0098544A3 (en
Inventor
Pierre Prevel
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NORMANDE DE RECHERCHE ET DE PARTICIPATION Ste
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NORMANDE DE RECHERCHE ET DE PARTICIPATION Ste
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Priority to AT83106432T priority Critical patent/ATE26136T1/en
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Publication of EP0098544A3 publication Critical patent/EP0098544A3/en
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Classifications

    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines

Definitions

  • the present invention relates to a process for the anti-felting treatment of undyed keratin fibers, of any origin, whatever the stage of preparation of the material, the aforementioned process comprising a basic oxidation catalyzed by a metal salt.
  • Certain methods are based on the chlorination of keratin fibers using chlorinated organic compounds and in the presence of metal salt, in particular of alkali metals, but the fibers thus treated have a rougher and less pleasant feel.
  • US Patent 2,599,977 teaches an anti-felting treatment of wool by impregnation with copper, nickel, silver or mercury compounds followed by a treatment with peroxides.
  • compositions comprising the combination of cationic compounds, especially quaternary ammonium compounds and surfactants.
  • compositions comprising prepolymers subsequently polymerized on the fiber, or alternatively fixing on the fiber resins of the cationic type.
  • the aforementioned methods have the drawback either of being too specific to the type of fibers treated, or of modifying the feel too far from the natural feel of the fiber, and more often than not being very expensive due to the ingredients used or the duration and complexity of the treatment.
  • the subject of the invention is an anti-felting process which respects as much as possible the structure of the treated keratin fiber, and largely preserves its initial qualities of feel, which is very much sought after by users.
  • the invention also relates to the implementation of a simple, rapid anti-felting process, and of a very general application to the various types of keratin fibers.
  • the invention finally relates to the treated keratin material, having remarkable anti-felting properties, while retaining qualities of touch very close to those of natural keratin material.
  • the process of the invention essentially consists in treating a keratin fiber in an aqueous medium with a very small quantity of a sufficiently soluble salt of a polyvalent metal, in the presence of a weak organic acid and under heat, so as to fix on the fiber a thin and continuous layer of the metal salt, to treat the fiber thus coated by heating in an aqueous oxidizing bath in the presence of an organic base, the fiber then being washed appropriately, and passed through an acid bath before wring it out and dry it.
  • the metal salt distributed in a thin layer around the keratin fiber has a catalytic action according to which, in basic oxidizing medium, would produce a surface modification of the fiber, with opening of the bridges of sulfur of the keratin and a partial rearrangement of the structure comprising bridges of sulfur and nitrogen.
  • the material thus obtained is treated with a purified water bath containing per 100 kg of material, 0.4 to 1.6 gram molecule and preferably 0.6 to 1.2 gram molecule of a soluble salt of a metal. at several valences, and after having acidified the bath with an organic acid until a pH of 3 to 4 is obtained, it is slowly heated to a temperature of 60 to 70 ° C. which is maintained with circulation of the bath for a sufficient period of time to obtain a homogeneous fixing of the metal salt on the fiber, the bath then being removed and the material rinsed with purified water.
  • the rinsed material thus obtained is treated with a purified water bath in the presence of an oxidizing agent which does not introduce a metal ion other than an alkali and an organic base, to obtain a pH of 8.5 to 9, and the bath is heated to a temperature of 45 to 50 ° C, while maintaining the pH in the above range, the bath then being removed and the material rinsed with cold purified water.
  • the rinsed material thus obtained is treated with a purified water bath containing a reducing agent which does not introduce a metal ion other than an alkali, and a sequestering agent, preferably hot at a temperature below 50 ° C., the bath then being discharged and the material rinsed with purified water.
  • the material thus obtained is treated with a purified water bath containing an organic acid until a pH of approximately 3 is obtained, with circulation for a period of time sufficient to obtain a homogeneous distribution of the acid, the material then being optionally either directly dyed or wrung and dried on acid.
  • purified water preferably deionized or bipermuted water, and in any case it must have a hydrotimetric degree lower than 15 French hydrotimetric degrees.
  • the keratin raw material is used in a form which is sufficiently dry pressed to avoid the preferential paths of circulation of the bath in the mass.
  • the detergent used is preferably a nonionic detergent such as a C 2 -C 4 alkylene oxide condensate on a molecule of a C 8 to C 30 aliphatic compound, such as for example a 5 to 15 moles of ethylene oxide and a C 10 to C 5 aliphatic alcohol, 5 , or a similar detergent, in an amount of about 1 to 2 g / liter of bath.
  • a nonionic detergent such as a C 2 -C 4 alkylene oxide condensate on a molecule of a C 8 to C 30 aliphatic compound, such as for example a 5 to 15 moles of ethylene oxide and a C 10 to C 5 aliphatic alcohol, 5 , or a similar detergent, in an amount of about 1 to 2 g / liter of bath.
  • ethylenediaamine compounds or the like are used in particular, and preferably ethylene diaminotetracetic acid or EDTA, in an amount of approximately 1 to 2 g / liter of bath.
  • trisodium phosphate is preferably used in an amount of about 0.5 to 1 g / liter of bath.
  • any other detergent or sequestering agent making it possible to obtain a similar result that is to say a material free of its natural or foreign impurities and in particular of metal salts other than alkalies, may be used. .
  • cupric or ferrous salts, aluminum, titanium or chromium salts are used as the salt of a metal with several valences sufficiently soluble in water at the treatment temperature.
  • cupric salts are used, in particular copper sulphate because of its high solubility and its low cost.
  • the amount of copper used in the form of cupric salt corresponds to 0.023 6-0.095% and preferably to 0.035-0.075% by weight of copper relative to the weight of keratin fibers.
  • ferrous salts, aluminum salts, titanium salts and chloride salts having sufficient solubility under the conditions of the bath used also give good results.
  • the aluminum salts, sulfate, chloride and nitrate among the ferrous salts chloride, nitrate and sulfate, among the titanium salts trichloride and oxalate, among the chromium salts chloride Cl 2 Cr, nitrate, oxalate and acetate.
  • an organic acid such as acetic acid, formic acid, citric acid or the like is used, acetic acid being preferred.
  • the temperature rise to 60 to 70 ° C. is carried out slowly with circulation of the bath so as to obtain the most homogeneous distribution possible, and the temperature is then maintained, still with circulation of the bath, until the fixing of the metal salt to the fiber is sufficient, which is possibly controlled by the evolution of the coloring of the bath or by any other assay method, in particular by potentiometry.
  • hydrogen peroxide at 130 volumes is preferably used in an amount necessary to obtain a bath corresponding to a content of 2 to 3 and preferably 2.5 volumes of oxygenated water, that is to say 6 at 9 and preferably about 7.6 g of hydrogen peroxide per liter, but it is also possible to use any oxidant or equivalent oxidizing system which does not introduce metal ions other than alkalines into the bath.
  • a C z -C 4 alkanolamine is preferably used, such as mono-, di- or tri-ethanolamine, the latter giving excellent results.
  • the pH is maintained in the range of 8.5 to 9 by addition of additional amounts of the organic base. Heating at a temperature of 45 to 50 ° C, during which a moderate release of oxygen takes place, is maintained for a period of 1 hour 30 to 2 hours for a total charge of the order of 1000 kg with a bath ratio of the order of 1: 10.
  • a reducing agent an alkaline hydrosulfite such as sodium hydrosulfite is preferably used, and as EDTA sequestering agent, it being understood that any other reducing agent which does not introduce metal ions other than alkali metals or any other agent sequestering metal ions. may also be suitable.
  • the process of the invention is carried out in the tank in an appropriate dyeing installation, preferably made of stainless steel, provided with good circulation of the bath with the possibility of reversing the circulation, avoiding too violent circulation as well as a too strong pressing of the material.
  • keratin fiber the most varied animal fibers can be used, in particular wool, rabbit hair, camel hair, cashmere, alpaca fabric, etc.
  • the fibers used are undyed fibers, which can be either unbleached or naturally colored. In the latter case, the original shade is modified: it is generally more or less lightened. The ecru are practically unchanged.
  • the treatment can be carried out on fibers in fluff or spun, woven or knitted.
  • the bath ratios that is to say “treated material: bath, can vary widely from 1: 5 to 1:20, but preferably a bath ratio of 1: 8 to 1 is used: 15.
  • the method of the invention makes it possible to obtain a natural fiber for which the felting is considerably reduced, and whose touch qualities remain practically unchanged.
  • the material obtained after the last treatment in acid bath can be dyed directly, or wrung out, dried and stored.
  • the bath is then evacuated and the material is thoroughly rinsed with purified water. This washing operation is repeated several times if necessary until a material free of its impurities is obtained.
  • a bath is prepared with purified water to which is added 100 g of copper sulphate (0.626 molecule) previously dissolved in a sufficient quantity of hot water. 900 g of concentrated acetic acid are then added, which makes it possible to obtain a pH of approximately 3-4, the bath is heated, with circulation, to the temperature of 70 ° over a period of 15 minutes, and the bath is maintained at this temperature for about 1 hour. The bath is drained and the material is rinsed with cold purified water.
  • the bath is prepared with purified water to which 18 liters of hydrogen peroxide at 130 volumes are added, so as to obtain approximately 900 liters of bath at approximately 2.5 volumes. Then added 4.5 kg of triethanolamine. The bath is heated to the temperature of 45 ° C over a period of about 15 minutes, with circulation, and the bath is maintained at this temperature for 2 hours, while adjusting the pH from 8.5 to 9 by possible additions of triethanolamine. A slight and regular release of oxygen is observed, the bath remaining practically colorless.
  • the bath is drained and the material is thoroughly rinsed with cold purified water.
  • the material is washed with a bath consisting of 900 liters of purified water containing 1.8 kg of sodium hydrosulfite and 0.450 kg of ethylenediaminotetraacetic acid in 40% aqueous solution.
  • the bath is heated to the temperature of 40 ° C, with circulation, and maintained at this temperature for 30 minutes.
  • the bath is drained and the material is thoroughly rinsed with cold purified water.
  • the material thus rinsed is treated with a bath consisting of 900 liters of purified water containing 0.9 kg of concentrated acetic acid, and this with circulation of the bath for 15 minutes. The bath is then discharged, the material is wrung and dried.
  • a “premium fineness” quality wool is thus obtained in flock having a high felting resistance.
  • the treatment is carried out under the same conditions as those indicated in Example 1, except that the etching is carried out with an amount of 1.232 mole of copper sulphate (200 g) per 100 kg of rabbit hair, and only in the oxidation stage in basic medium, 5.4 kg of triethanolamine is used for 900 liters of bath.
  • Examples 1 and 2 are repeated except that copper sulphate is replaced by chloride respectively iron II, aluminum sulfate, titanium trichloride and chromium chloride II. Good results are also obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

Antifelting treatment of keratinous fibres according to which the material is freed of its natural or foreign impurities by an aqueous detergent bath containing at least one metal ion sequestering agent; the rinsed material is treated by a water-soluble salt of a metal having several valencies, hot, in an aqueous bath of pH 3 to 4 during a sufficient period of time to achieve the homogeneous fixing of the metal salt on the fibre; the rinsed material is treated with an aqueous bath in the presence of an oxidizing agent which does not introduce metal ions and of an organic base at a pH of 8.5 to 9, hot, for 1 hour 30 minutes to 2 hours; the rinsed material is treated with an aqueous bath containing a reducing agent which does not introduce metal ions and a sequestering agent, to eliminate the ingredients used; and the material obtained is treated by an aqueous bath at pH 3, the material being subsequently drained and dried over acid. A keratinous material is thus obtained for which felting is considerably reduced and the feel qualities of which remain practically unchanged.

Description

La présente invention concerne un procédé de traitement anti-feutrage de fibres kératiniques non teintes, de toute origine, quel que soit le stade d'élaboration de la matière, le procédé précité comprenant une oxydation basique catalysée par un sel métallique.The present invention relates to a process for the anti-felting treatment of undyed keratin fibers, of any origin, whatever the stage of preparation of the material, the aforementioned process comprising a basic oxidation catalyzed by a metal salt.

Au cours des diverses opérations de tissage, et du fait du vieillissement par suite notamment des lavages et de l'usure, on observe, pour les tissus n'ayant subi aucun traitement pour l'éviter, un feutrage plus ou moins marqué qui diminue considérablement les qualités et la valeur de ces tissus, notamment dans la confection des vêtements.During the various weaving operations, and due to aging, in particular as a result of washing and wear, we observe, for fabrics which have not undergone any treatment to avoid it, a more or less marked felting which considerably decreases the qualities and value of these fabrics, especially in the making of clothing.

On connaît de nombreux procédés en vue de supprimer le plus possible le feutrage des fibres et des tissus en général.Numerous methods are known with a view to suppressing the felting of fibers and fabrics in general as much as possible.

Certains procédés sont basés sur la chloruration des fibres kératiniques à l'aide de composés organiques chlorés et en présence de sel métallique en particulier de métaux alcalins, mais les fibres ainsi traitées ont un toucher plus rèche et moins agréable.Certain methods are based on the chlorination of keratin fibers using chlorinated organic compounds and in the presence of metal salt, in particular of alkali metals, but the fibers thus treated have a rougher and less pleasant feel.

Le brevet US 2 599 977 enseigne un traitement anti-feutrage de la laine par imprégnation avec des composés de cuivre, nickel, argent ou mercure suivi d'un traitement aux peroxydes.US Patent 2,599,977 teaches an anti-felting treatment of wool by impregnation with copper, nickel, silver or mercury compounds followed by a treatment with peroxides.

D'autres procédés utilisent des compositions comprenant l'association de composés cationiques, notamment de composés d'ammonium quaternaire et d'agents de surface.Other methods use compositions comprising the combination of cationic compounds, especially quaternary ammonium compounds and surfactants.

D'autres procédés utilisent aussi des compositions comprenant des prépolymères ultérieurement polymérisés sur la fibre, ou encore la fixation sur la fibre de résines du type cationique.Other methods also use compositions comprising prepolymers subsequently polymerized on the fiber, or alternatively fixing on the fiber resins of the cationic type.

Les procédés précités présentent l'inconvénient, soit d'être trop spécifiques au type de fibres traitées, soit de modifier le toucher d'une façon trop éloignée du toucher naturel de la fibre, et le plus souvent d'être très onéreux du fait des ingrédients utilisés ou de la durée et de la complexité du traitement.The aforementioned methods have the drawback either of being too specific to the type of fibers treated, or of modifying the feel too far from the natural feel of the fiber, and more often than not being very expensive due to the ingredients used or the duration and complexity of the treatment.

L'invention a pour objet un procédé anti-feutrage respectant le plus possible la structure de la fibre kératinique traitée, et préservant largement ses qualités initiales de toucher, ce qui est très recherché par les utilisateurs.The subject of the invention is an anti-felting process which respects as much as possible the structure of the treated keratin fiber, and largely preserves its initial qualities of feel, which is very much sought after by users.

L'invention a également pour objet la mise en oeuvre d'un procédé anti-feutrage simple, rapide, et d'une application très générale aux divers types de fibres kératiniques.The invention also relates to the implementation of a simple, rapid anti-felting process, and of a very general application to the various types of keratin fibers.

L'invention a enfin pour objet la matière kératinique traitée, présentant des propriétés anti-feutrage remarquables, tout en conservant des qualités de toucher très voisines de celles de la matière kératinique naturelle.The invention finally relates to the treated keratin material, having remarkable anti-felting properties, while retaining qualities of touch very close to those of natural keratin material.

Le procédé de l'invention consiste essentiellement à traiter une fibre kératinique, en milieu aqueux avec une très faible quantité d'un sel suffisamment soluble d'un métal polyvalent, en présence d'un acide organique faible et à chaud, de façon à fixer sur la fibre une couche mince et continue du sel métallique, à traiter la fibre ainsi revêtue par chauffage dans un bain aqueux oxydant en présence d'une base organique, la fibre étant ensuite lavée de façon appropriée, et passée dans un bain acide avant de l'essorer et de la sécher.The process of the invention essentially consists in treating a keratin fiber in an aqueous medium with a very small quantity of a sufficiently soluble salt of a polyvalent metal, in the presence of a weak organic acid and under heat, so as to fix on the fiber a thin and continuous layer of the metal salt, to treat the fiber thus coated by heating in an aqueous oxidizing bath in the presence of an organic base, the fiber then being washed appropriately, and passed through an acid bath before wring it out and dry it.

Bien que le mécanisme procurant le résultat anti-feutrant recherché ne soit pas encore bien établi, il semble que le sel métallique réparti en une couche mince autour de la fibre de kératine ait une action catalytique selon laquelle, en milieu oxydant basique, se produirait une modification superficielle de la fibre, avec ouverture des ponts de soufre de la kératine et un réarrangement partiel de la structure comprenant des ponts de soufre et d'azote.Although the mechanism providing the desired anti-felting result is not yet well established, it seems that the metal salt distributed in a thin layer around the keratin fiber has a catalytic action according to which, in basic oxidizing medium, would produce a surface modification of the fiber, with opening of the bridges of sulfur of the keratin and a partial rearrangement of the structure comprising bridges of sulfur and nitrogen.

De façon plus précise, on effectue le traitement selon les stades suivants :

  • On mouille à froid la matière, préalablement pressée à sec, avec de l'eau épurée contenant un agent détersif, et après l'addition d'un séquestrant des ions métalliques, et éventuellement d'un phosphate alcalin si la matière est très sale, on effectue un lavage à la température de 40 à 55 °C avec circulation du bain pendant un laps de temps suffisant pour obtenir une matière débarrassée de ses impuretés naturelles ou étrangères, après quoi on évacue le bain et on rince la matière à l'eau épurée.
More precisely, the treatment is carried out according to the following stages:
  • The material is wetted cold, previously dry pressed, with purified water containing a detersive agent, and after the addition of a sequestering agent of metal ions, and optionally an alkaline phosphate if the material is very dirty, washing is carried out at a temperature of 40 to 55 ° C. with circulation of the bath for a sufficient period of time to obtain a material free of its natural or foreign impurities, after which the bath is removed and the material is rinsed with water refined.

On traite la matière ainsi obtenue avec un bain d'eau épurée contenant pour 100 kg de matière, 0,4 à 1,6 molécule gramme et de préférence 0,6 à 1,2 molécule gramme d'un sel soluble d'un métal à plusieurs valences, et après avoir acidifié le bain avec un acide organique jusqu'à l'obtention d'un pH de 3 à 4, on le chauffe lentement jusqu'à une température de 60 à 70 °C que l'on maintient avec circulation du bain pendant un laps de temps suffisant pour obtenir une fixation homogène du sel métallique sur la fibre, le bain étant ensuite évacué et la matière rincée à l'eau épurée.The material thus obtained is treated with a purified water bath containing per 100 kg of material, 0.4 to 1.6 gram molecule and preferably 0.6 to 1.2 gram molecule of a soluble salt of a metal. at several valences, and after having acidified the bath with an organic acid until a pH of 3 to 4 is obtained, it is slowly heated to a temperature of 60 to 70 ° C. which is maintained with circulation of the bath for a sufficient period of time to obtain a homogeneous fixing of the metal salt on the fiber, the bath then being removed and the material rinsed with purified water.

On traite la matière rincée ainsi obtenue, par un bain d'eau épurée en présence d'un agent oxydant n'introduisant pas d'ion métallique autre qu'alcalin et d'une base organique, pour obtenir un pH de 8,5 à 9, et l'on chauffe le bain à une température de 45 à 50 °C, tout en maintenant le pH dans la gamme précitée, le bain étant ensuite évacué et la matière rincée à l'eau épurée froide.The rinsed material thus obtained is treated with a purified water bath in the presence of an oxidizing agent which does not introduce a metal ion other than an alkali and an organic base, to obtain a pH of 8.5 to 9, and the bath is heated to a temperature of 45 to 50 ° C, while maintaining the pH in the above range, the bath then being removed and the material rinsed with cold purified water.

On traite la matière rincée ainsi obtenue, par un bain d'eau épurée contenant un agent réducteur n'introduisant pas d'ion métallique autre qu'alcalin, et un agent séquestrant, de préférence à chaud à une température inférieure à 50°C, le bain étant ensuite évacué et la matière rincée à l'eau épurée.The rinsed material thus obtained is treated with a purified water bath containing a reducing agent which does not introduce a metal ion other than an alkali, and a sequestering agent, preferably hot at a temperature below 50 ° C., the bath then being discharged and the material rinsed with purified water.

On traite enfin la matière ainsi obtenue, par un bain d'eau épurée contenant un acide organique jusqu'à l'obtention d'un pH de 3 environ, avec circulation pendant un laps de temps suffisant pour obtenir une répartition homogène de l'acide, la matière étant ensuite éventuellement soit teinte directement, soit essorée et séchée sur acide.Finally, the material thus obtained is treated with a purified water bath containing an organic acid until a pH of approximately 3 is obtained, with circulation for a period of time sufficient to obtain a homogeneous distribution of the acid, the material then being optionally either directly dyed or wrung and dried on acid.

Il est essentiel d'utiliser, dans chacun des stades du procédé, de l'eau épurée de préférence de l'eau déionisée ou bipermutée, et de toute façon elle doit avoir un degré hydrotimétrique inférieur à 15 degrés hydrotimétrique français.It is essential to use, in each stage of the process, purified water, preferably deionized or bipermuted water, and in any case it must have a hydrotimetric degree lower than 15 French hydrotimetric degrees.

On utilise la matière première kératinique sous une forme suffisamment pressée à sec pour éviter les chemins préférentiels de circulation du bain dans la masse.The keratin raw material is used in a form which is sufficiently dry pressed to avoid the preferential paths of circulation of the bath in the mass.

L'agent détersif utilisé est de préférence détersif non-ionique tel qu'un condensat d'oxyde d'alcoylène en C2 à C4 sur une molécule d'un composé aliphatique en C8 à C30, comme par exemple un condensat de 5 à 15 moles d'oxyde d'éthylène et d'un alcool aliphatique en C10 à C,5, ou un détersif analogue, en une quantité d'environ 1 à 2 g/litre de bain.The detergent used is preferably a nonionic detergent such as a C 2 -C 4 alkylene oxide condensate on a molecule of a C 8 to C 30 aliphatic compound, such as for example a 5 to 15 moles of ethylene oxide and a C 10 to C 5 aliphatic alcohol, 5 , or a similar detergent, in an amount of about 1 to 2 g / liter of bath.

Comme agent séquestrant des ions métalliques on utilise notamment des composés de l'éthylènedia- mine ou des composés analogues, et de préférence l'acide éthylène diaminotétracétique ou EDTA, en une quantité d'environ 1 à 2 g/litre de bain.As the metal ion sequestering agent, ethylenediaamine compounds or the like are used in particular, and preferably ethylene diaminotetracetic acid or EDTA, in an amount of approximately 1 to 2 g / liter of bath.

Comme phosphate alcalcin on utilise de préférence le phosphate trisodique en une quantité d'environ 0,5 à 1 g/litre de bain.As alkaline phosphate, trisodium phosphate is preferably used in an amount of about 0.5 to 1 g / liter of bath.

Pour effectuer ce stade de lavage initial, on peut utiliser tout autre agent détersif ou séquestrant permettant d'obtenir un résultat analogue, c'est-à-dire une matière débarrassée de ses impuretés naturelles ou étrangères et notamment de sels métalliques autres qu'alcalins.To carry out this initial washing stage, any other detergent or sequestering agent making it possible to obtain a similar result, that is to say a material free of its natural or foreign impurities and in particular of metal salts other than alkalies, may be used. .

Dans le stade de mordançage, on utilise comme sel d'un métal à plusieurs valences suffisamment soluble dans l'eau à la température du traitement, des sels cuivriques ou des sels ferreux, des sels d'aluminium, de titane ou de chrome. Selon un mode de réalisation, on utilise des sels cuivriques, notamment le sulfate de cuivre en raison de sa grande solubilité et de son coût faible. La quantité de cuivre utilisé sous forme de sel cuivrique correspond à 0,023 6-0,095 % et de préférence à 0,035-0,075 % en poids de cuivre par rapport au poids des fibres kératiniques.In the etching stage, cupric or ferrous salts, aluminum, titanium or chromium salts are used as the salt of a metal with several valences sufficiently soluble in water at the treatment temperature. According to one embodiment, cupric salts are used, in particular copper sulphate because of its high solubility and its low cost. The amount of copper used in the form of cupric salt corresponds to 0.023 6-0.095% and preferably to 0.035-0.075% by weight of copper relative to the weight of keratin fibers.

Toutefois, les sels ferreux, les sels d'aluminium, les sels de titane et les sels de chlorure ayant une solubilité suffisante dans les conditions du bain utilisé donnent également de bons résultats.However, ferrous salts, aluminum salts, titanium salts and chloride salts having sufficient solubility under the conditions of the bath used also give good results.

On utilise avantageusement parmi les sels d'aluminium, le sulfate, le chlorure et le nitrate ; parmi les sels ferreux le chlorure, le nitrate et le sulfate, parmi les sels de titane le trichlorure et l'oxalate, parmi les sels de chrome le chlorure Cl2Cr, le nitrate, l'oxalate et l'acétate.Advantageously used among the aluminum salts, sulfate, chloride and nitrate; among the ferrous salts chloride, nitrate and sulfate, among the titanium salts trichloride and oxalate, among the chromium salts chloride Cl 2 Cr, nitrate, oxalate and acetate.

Pour obtenir l'acidification du bain de mordançage jusqu'à pH 3 à 4, on utilise un acide organique comme l'acide acétique, l'acide formique, l'acide citrique ou un acide analogue, l'acide acétique étant préféré.To obtain the acidification of the etching bath to pH 3 to 4, an organic acid such as acetic acid, formic acid, citric acid or the like is used, acetic acid being preferred.

La montée en température jusqu'à 60 à 70 °C, s'effectue lentement avec circulation du bain de façon à obtenir une répartition la plus homogène possible, et la température est ensuite maintenue, toujours avec circulation du bain, jusqu'à ce que la fixation du sel métallique sur la fibre soit suffisante, ce qui est éventuellement contrôlé par l'évolution de la coloration du bain ou par toute autre méthode de dosage, notamment par potentiométrie.The temperature rise to 60 to 70 ° C. is carried out slowly with circulation of the bath so as to obtain the most homogeneous distribution possible, and the temperature is then maintained, still with circulation of the bath, until the fixing of the metal salt to the fiber is sufficient, which is possibly controlled by the evolution of the coloring of the bath or by any other assay method, in particular by potentiometry.

Comme oxydant on utilise de préférence de l'eau oxygénée à 130 volumes en une quantité nécessaire pour obtenir un bain correspondant à une teneur de 2 à 3 et de préférence 2,5 volumes d'eau oxygénée, c'est-à-dire 6 à 9 et de préférence environ 7,6 g d'eau oxygénée par litre, mais on peut également utiliser tout oxydant ou système oxydant équivalent n'introduisant pas dans le bain d'ions métalliques autres qu'alcalins.As oxidizing agent, hydrogen peroxide at 130 volumes is preferably used in an amount necessary to obtain a bath corresponding to a content of 2 to 3 and preferably 2.5 volumes of oxygenated water, that is to say 6 at 9 and preferably about 7.6 g of hydrogen peroxide per liter, but it is also possible to use any oxidant or equivalent oxidizing system which does not introduce metal ions other than alkalines into the bath.

Comme base organique on utilise de préférence une alcanolamine en Cz-C4, telle que la mono-, la di-ou la tri-éthanolamine, cette dernière donnant d'excellents résultats.As organic base, a C z -C 4 alkanolamine is preferably used, such as mono-, di- or tri-ethanolamine, the latter giving excellent results.

Le pH est maintenu dans la gamme de 8,5 à 9 par addition de quantités supplémentaires de la base organique. Le chauffage à la température de 45 à 50 °C, au cours duquel s'effectue un dégagement modéré d'oxygène, est maintenu pendant un laps de temps de 1 heure 30 à 2 heures pour une charge totale de l'ordre de 1 000 kg avec un rapport de bain de l'ordre de 1 : 10.The pH is maintained in the range of 8.5 to 9 by addition of additional amounts of the organic base. Heating at a temperature of 45 to 50 ° C, during which a moderate release of oxygen takes place, is maintained for a period of 1 hour 30 to 2 hours for a total charge of the order of 1000 kg with a bath ratio of the order of 1: 10.

Le lavage effectué en présence d'un agent réducteur et d'un agent séquestrant a pour but de débarrasser complètement la matière des ingrédients utilisés dans les traitements précédents. Comme réducteur on utilise de préférence un hydrosulfite alcalin tel que l'hydrosulfite de soude et comme séquestrant l'EDTA, étant entendu que tout autre agent réducteur n'introduisant pas d'ions métalliques autres qu'alcalins ou tout autre agent séquestrant des ions métalliques peut également convenir.The purpose of washing in the presence of a reducing agent and a sequestering agent is to completely rid the material of the ingredients used in the preceding treatments. As reducing agent, an alkaline hydrosulfite such as sodium hydrosulfite is preferably used, and as EDTA sequestering agent, it being understood that any other reducing agent which does not introduce metal ions other than alkali metals or any other agent sequestering metal ions. may also be suitable.

Le procédé de l'invention s'effectue à la cuve dans une installation de teinture appropriée, de préférence en inox, munie d'une bonne circulation du bain avec possibilité d'inverser la circulation, en évitant une circulation trop violente ainsi qu'un pressage trop puissant de la matière.The process of the invention is carried out in the tank in an appropriate dyeing installation, preferably made of stainless steel, provided with good circulation of the bath with the possibility of reversing the circulation, avoiding too violent circulation as well as a too strong pressing of the material.

Comme fibre kératinique on peut utiliser des fibres animales les plus variées, notamment la laine, les poils de lapin, de chameau, des tissus de cachemire, d'alpaga, etc...As keratin fiber, the most varied animal fibers can be used, in particular wool, rabbit hair, camel hair, cashmere, alpaca fabric, etc.

Les fibres utilisées sont des fibres non teintes, pouvant être soit écrues, soit colorées naturellement. Dans ce dernier cas la nuance d'origine est modifiée : elle est généralement plus ou moins éclaircie. Les écrus ne sont pratiquement pas modifiés.The fibers used are undyed fibers, which can be either unbleached or naturally colored. In the latter case, the original shade is modified: it is generally more or less lightened. The ecru are practically unchanged.

Le traitement peut être effectué sur des fibres en bourre ou filées, tissées ou tricotées. Selon la présentation de la matière, les rapports de bain c'est-à-dire « matière traitée : bain peuvent varier largement de 1 : 5 à 1 : 20 mais de préférence on utilise un rapport de bain de 1 : 8 à 1 : 15.The treatment can be carried out on fibers in fluff or spun, woven or knitted. Depending on the presentation of the material, the bath ratios, that is to say “treated material: bath, can vary widely from 1: 5 to 1:20, but preferably a bath ratio of 1: 8 to 1 is used: 15.

Le procédé de l'invention permet d'obtenir une fibre naturelle pour laquelle le feutrage est considérablement diminué, et dont les qualités de toucher restent pratiquement inchangées.The method of the invention makes it possible to obtain a natural fiber for which the felting is considerably reduced, and whose touch qualities remain practically unchanged.

La matière obtenue après le dernier traitement en bain acide peut être teinte directement, ou bien essorée, séchée et stockée.The material obtained after the last treatment in acid bath can be dyed directly, or wrung out, dried and stored.

Les exemples suivants dans lesquels, sauf indication contraire, les pourcentages sont indiqués en poids et les températures en degrés centigrades, permettront de mieux comprendre l'objet de l'invention.The following examples in which, unless otherwise indicated, the percentages are given by weight and the temperatures in degrees centigrade, will allow a better understanding of the subject of the invention.

Exemple 1 : Traitement anti-feutrage d'une laine du type « finesse prime en bourreEXAMPLE 1 Anti-Felting Treatment of a Wool of the "Premium Fineness in Filler" LavageWashing

Dans un appareil en inox à circulation par pompe ayant une capacité utile d'environ 1000 litres, on charge 100 kg de matière pressée à sec dans le panier de l'appareil, on la mouille à la température de 20 °C avec de l'eau épurée, et l'on complète le bain jusqu'à 900 litres d'eau épurée, en ajoutant 1,2 kg du produit de réaction d'un alcanol primaire en C12 avec 10 molécules d'oxyde d'éthylène, ainsi que 0,9 kg d'une solution à 40 % d'acide éthylène diaminotétracétique ou EDTA et 0,450 kg de phosphate trisodique. On chauffe le bain à la température de 40 à 45 °C et on le maintient avec circulation à cette température pendant un laps de temps d'environ 30 minutes.In a stainless steel device with circulation by pump having a useful capacity of approximately 1000 liters, 100 kg of dry pressed material are loaded into the basket of the device, it is wetted at the temperature of 20 ° C. with purified water, and the bath is completed up to 900 liters of purified water, adding 1.2 kg of the reaction product of a primary C 12 alkanol with 10 molecules of ethylene oxide, as well as 0.9 kg of a 40% solution of ethylene diaminotetracetic acid or EDTA and 0.450 kg of trisodium phosphate. The bath is heated to the temperature of 40 to 45 ° C and maintained with circulation at this temperature for a period of time of approximately 30 minutes.

On évacue ensuite le bain et l'on rince abondamment la matière à l'eau épurée. Cette opération de lavage est répétée plusieurs fois si nécessaire jusqu'à l'obtention d'une matière débarrassée de ses impuretés.The bath is then evacuated and the material is thoroughly rinsed with purified water. This washing operation is repeated several times if necessary until a material free of its impurities is obtained.

MordançageEtching

On prépare un bain avec de l'eau épurée à laquelle on ajoute 100 g de sulfate de cuivre (0,626 molécule) préalablement dissous dans une quantité suffisante d'eau chaude. On ajoute ensuite 900 g d'acide acétique concentré ce qui permet d'obtenir un pH d'environ 3-4, on chauffe le bain, avec circulation, jusqu'à la température de 70° en un laps de temps de 15 minutes, et l'on maintient le bain à cette température pendant environ 1 heure. On évacue le bain et on rince la matière à l'eau épurée froide.A bath is prepared with purified water to which is added 100 g of copper sulphate (0.626 molecule) previously dissolved in a sufficient quantity of hot water. 900 g of concentrated acetic acid are then added, which makes it possible to obtain a pH of approximately 3-4, the bath is heated, with circulation, to the temperature of 70 ° over a period of 15 minutes, and the bath is maintained at this temperature for about 1 hour. The bath is drained and the material is rinsed with cold purified water.

Oxydation en présence d'une base organiqueOxidation in the presence of an organic base

On prépare le bain avec de l'eau épurée à laquelle on ajoute 18 litres d'eau oxygénée à 130 volumes, de façon à obtenir environ 900 litres de bain à environ 2,5 volumes. On ajoute ensuite 4,5 kg de triéthanolamine. On chauffe le bain à la température de 45 °C en un laps de temps d'environ 15 minutes, avec circulation, et l'on maintient le bain à cette température pendant 2 heures, tout en ajustant le pH de 8,5 à 9 par des additions éventuelles de triéthanolamine. On observe un dégagement faible et régulier d'oxygène, le bain restant pratiquement incolore.The bath is prepared with purified water to which 18 liters of hydrogen peroxide at 130 volumes are added, so as to obtain approximately 900 liters of bath at approximately 2.5 volumes. Then added 4.5 kg of triethanolamine. The bath is heated to the temperature of 45 ° C over a period of about 15 minutes, with circulation, and the bath is maintained at this temperature for 2 hours, while adjusting the pH from 8.5 to 9 by possible additions of triethanolamine. A slight and regular release of oxygen is observed, the bath remaining practically colorless.

On évacue le bain et l'on rince abondamment la matière à l'eau épurée froide.The bath is drained and the material is thoroughly rinsed with cold purified water.

Lavage de fin de traitementEnd of treatment wash

On lave la matière avec un bain constitué par 900 litres d'eau épurée contenant 1,8 kg d'hydrosulfite de soude et 0,450 kg d'acide éthylènediaminotétraacétique en solution aqueuse à 40 %. On chauffe le bain jusqu'à la température de 40 °C, avec circulation, et on le maintient à cette température pendant 30 minutes. On évacue le bain et l'on rince abondamment la matière avec de l'eau épurée froide.The material is washed with a bath consisting of 900 liters of purified water containing 1.8 kg of sodium hydrosulfite and 0.450 kg of ethylenediaminotetraacetic acid in 40% aqueous solution. The bath is heated to the temperature of 40 ° C, with circulation, and maintained at this temperature for 30 minutes. The bath is drained and the material is thoroughly rinsed with cold purified water.

Lavage finalFinal wash

On traite la matière ainsi rincée avec un bain constitué par 900 litres d'eau épurée contenant 0,9 kg d'acide acétique concentré, et cela avec circulation du bain pendant 15 minutes. On évacue ensuite le bain, on essore la matière et on la sèche.The material thus rinsed is treated with a bath consisting of 900 liters of purified water containing 0.9 kg of concentrated acetic acid, and this with circulation of the bath for 15 minutes. The bath is then discharged, the material is wrung and dried.

On obtient ainsi une laine de qualité « finesse prime » en bourre ayant une grande résistance au feutrage.A “premium fineness” quality wool is thus obtained in flock having a high felting resistance.

On obtient des résultats tout à fait analogues, notamment avec les poils de chameau ou d'alpaga.Very similar results are obtained, especially with camel or alpaca hair.

Exemple 2 : Traitement anti-feutrant de poils de lapinEXAMPLE 2 Anti-Felting Treatment of Rabbit Hair

On effectue le traitement dans les mêmes conditions que celles indiquées dans l'exemple 1, sauf qu'on effectue le mordançage avec une quantité de 1,232 mole de sulfate de cuivre (200 g) pour 100 kg de poils de lapin, et que dans le stade d'oxydation en milieu basique, on utilise 5,4 kg de triéthanolamine pour 900 litres de bain.The treatment is carried out under the same conditions as those indicated in Example 1, except that the etching is carried out with an amount of 1.232 mole of copper sulphate (200 g) per 100 kg of rabbit hair, and only in the oxidation stage in basic medium, 5.4 kg of triethanolamine is used for 900 liters of bath.

A la fin du traitement on obtient un poil de lapin ayant d'excellentes propriétés anti-feutrage.At the end of the treatment, a rabbit hair is obtained having excellent anti-felting properties.

Exemples 3 à 10Examples 3 to 10

On répète les exemples 1 et 2 sauf qu'on remplace le sulfate de cuivre respectivement par le chlorure de fer II, le sulfate d'aluminium, le trichlorure de titane et le chlorure de chrome Il. On obtient également de bons résultats.Examples 1 and 2 are repeated except that copper sulphate is replaced by chloride respectively iron II, aluminum sulfate, titanium trichloride and chromium chloride II. Good results are also obtained.

Claims (14)

1. Antifelting treatment process for keratinic fibres, comprising a preliminary wash, a pass through a bath containing a water-soluble salt of a metal, followed by a pass through a bath containing an oxidizing agent in the presence of a basic compound and a wash to finish the treatment, followed by a pass through an acidic bath, this process being characterized in that :
1) the material, pressed dry beforehand, is wetted cold with purified water containing a detergent and it is freed from its natural or foreign impurities by a hot wash in a bath of purified water containing detergent agents in the presence of at least one sequestering agent for metal ions and, if desired, an alkali metal phosphate, the bath being then discharged and the material being rinsed with purified water ;
2) the rinsed material thus produced is treated with a bath of purufied water containing, per 100 kg of material, 0.4 to 1.6 mole and preferably 0.6 to 1.2 mole of a water-soluble salt of a polyvalent metal chosen from cupric salts, ferrous salts, aluminium salts, titanium salts and chromium salts having a pH of 3 to 4 obtained by adding an organic acid, heated to a temperature of 60 to 70 °C with circulation of the bath for a sufficient period of time to obtain homogeneous bonding of the metal salt onto the fibre, the bath being then discharged and the material rinsed with purified water ;
3) the rinsed material thus obtained is treated with a bath of purified water in the presence of an oxidizing agent which does not introduce any metal ion other than an alkali metal ion, and an organic base, to obtain a pH of 8.5 to 9, at a temperature from 45 to 50 °C for a period of time of 1 hour 30 to 2 hours, while maintaining the pH in the abovementioned range by adding the organic base, the bath being then discharged and the material rinsed with cold purified water ;
4) the rinsed material thus obtained is treated with a bath of purified water containing a reducing agent which does not introduce any metal ion other than an alkali metal ion, together with a sequestering agent, preferably hot, until the ingredients used in the treatment are removed, the bath being then discharged and the material rinsed with purified water ; and
5) the material thus obtained is treated with a bath of purified water having a pH of approximately 3 obtained by the addition of an organic acid, with circulation for a sufficient period of time to obtain a homogeneous acid distribution, the material being then, if desired, either dyed directly or dewatered and dried after treatment with the acid, the purified water used in the process having a hardness of less than 15 degrees on the French hardness scale.
2. Process according to Claim 1, characterized in that the water-soluble metal salt used is a copper salt.
3. Process according to Claim 1, characterized in that the water-soluble salt used is copper sulphate.
4. Process according to Claim 1, characterized in that the organic acid used is acetic acid, formic acid or citric acid.
5. Process according to Claim 1, characterized in that hydrogen peroxide is used as oxidizing agent.
6. Process according to Claim 1, characterized in that the organic base used is a C2-C4 alkanolamine.
7. Process according to Claim 1, characterized in that the organic base is chosen from monoethanolamine, diethanolamine and triethanolamine.
8. Process according to Claim 1, characterized in that an alkali metal dithionite is used as reducing agent.
9. Process according to Claim 1, characterized in that a water-soluble salt chosen from ferrous salts, aluminium salts, titanium salts and chromium salts is used.
EP83106432A 1982-07-07 1983-07-01 Process for the anti-felt treatment of keratinous fibres consisting of a basic oxidation catalyzed by a metal salt, and fibres obtained according to the process Expired EP0098544B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83106432T ATE26136T1 (en) 1982-07-07 1983-07-01 ANTI-FELT TREATMENT PROCESS FOR KERATINE FIBERS INVOLVING BASIC OXIDATION CATALYZED BY A METAL SALT AND FIBERS THUS OBTAINED.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8211950A FR2529921A1 (en) 1982-07-07 1982-07-07 PROCESS FOR ANTI-FELT TREATMENT OF KERATIN FIBERS, COMPRISING BASIC OXIDATION CATALYZED BY A METALLIC SALT, AND FIBERS THUS OBTAINED
FR8211950 1982-07-07

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EP0098544A2 EP0098544A2 (en) 1984-01-18
EP0098544A3 EP0098544A3 (en) 1984-03-07
EP0098544B1 true EP0098544B1 (en) 1987-03-25

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US5490865A (en) * 1994-07-25 1996-02-13 Scheiwiller; Jurg P. Method of treating and dyeing animal fibers
US6879615B2 (en) * 2000-01-19 2005-04-12 Joseph Reid Henrichs FCSEL that frequency doubles its output emissions using sum-frequency generation
JP6055694B2 (en) * 2013-02-19 2016-12-27 丸三綿業株式会社 Method for cleaning cashmere raw fiber
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US2914374A (en) * 1954-03-24 1959-11-24 Harris Res Lab Inc Bleaching of keratinous fibrous material
US3156654A (en) * 1961-06-19 1964-11-10 Shell Oil Co Bleaching
FR1435360A (en) * 1965-05-07 1966-04-15 Prec Processes Textiles Ltd Continuous process to make wool resistant to shrinkage using a halogen-free oxidizing agent
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EP0098544A2 (en) 1984-01-18
EP0098544A3 (en) 1984-03-07
FR2529921A1 (en) 1984-01-13
DE3370498D1 (en) 1987-04-30
ATE26136T1 (en) 1987-04-15
JPS5976968A (en) 1984-05-02
US4492585A (en) 1985-01-08
FR2529921B1 (en) 1985-05-17

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