EP0098544B1 - Verfahren zur Antifilzbehandlung von Keratinfasern, eine basische, durch ein Metallsalz katalysierte Oxydation beinhaltend und auf diese Weise erhaltene Fasern - Google Patents

Verfahren zur Antifilzbehandlung von Keratinfasern, eine basische, durch ein Metallsalz katalysierte Oxydation beinhaltend und auf diese Weise erhaltene Fasern 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
European Patent Office
Prior art keywords
bath
purified water
rinsed
treated
salts
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83106432A
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English (en)
French (fr)
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EP0098544A3 (en
EP0098544A2 (de
Inventor
Pierre Prevel
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NORMANDE DE RECHERCHE ET DE PARTICIPATION Ste
Original Assignee
NORMANDE DE RECHERCHE ET DE PARTICIPATION Ste
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Priority to AT83106432T priority Critical patent/ATE26136T1/de
Publication of EP0098544A2 publication Critical patent/EP0098544A2/de
Publication of EP0098544A3 publication Critical patent/EP0098544A3/fr
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Publication of EP0098544B1 publication Critical patent/EP0098544B1/de
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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)

Claims (14)

1. Verfahren zur Filzfestbehandlung von Keratinfasern, bestehend aus einer vorhergehenden Wäsche, einem Durchgang durch ein Bad mit einem wasserlöslichen Metallsalz, einem Durchgang durch ein weiteres Bad mit einem Oxydationsmittel in Gegenwart einer basischen Verbindung, einer Wäsche zur Beendigung der Behandlung und einem weiteren Durchgang durch ein saures Bad, dadurch gekennzeichnet, dass man
1) das forerst trocken gepresste Material mit kaltem gereinigtem, ein Waschmittel enthaltendem Wasser benetzt wird und durch eine heisse Wäsche in einem Bad aus gereinigtem Wasser, das Waschmittel in Gegenwart mindestens eines Komplexbildners für Metallionen und gegebenenfalls eines Alkaliphosphats enthält, von seinen natürlichen oder fremden Verunreinigungen befreit, wird wobei das Bad dann abgelassen und das Material mit gereinigtem Wasser gespült wird,
2) das dabei erhaltene gespülte Material mit einem Bad aus gereinigtem Wasser, das auf 100 kg material 0,4 bis 1,6 Mol und vorzugsweise 0,6 bis 1,2 Mol eines wasserlöslichen Salzes eines mehrwertigen Metalls, das unter Cuprisalzen, Ferrosalzen, Aluminiumsalzen, Titansalzen und Chromsalzen ausgewählt ist, enthält, bei einem durch Zusatz einer organischen Säure erhaltenen pH von 3 bis 4 behandelt, auf eine Temperatur von 60 bis 70 °C unter Badumlauf genügend lang erhitzt, um homogene Bindung der Metallsalze an die Faser zu erzielen, das Bad dann ablässt und das Material mit gereinigtem Wasser spült,
3) das so erhaltene gespülte Material mit einem Bad aus gereinigtem Wasser in Gegenwart eines Oxydationsmittels, das kein Metallion einführt ausser Alkalimetall, und einer organischen Base, um einen pH von 8,5 bis 9 zu erhalten, bei einer Temperatur von 45 bis 50 °C für einen Zeitraum von 1 1/2 bis 2 Stunden unter Aufrechterhaltung des pH im obigen Bereich durch Zusatz organischer Base behandelt, danach das Bad ablässt und das Material mit gereinigtem Wasser spült,
4) das so erhaltene gespülte Material mit einem Bad aus gereinigtem Wasser, das ein Reduktionsmittel, das kein Metallion ausser Alkali einführt, und einen Komplexbildner enthält, vorzugsweise in der Hitze bis zur Entfernung der bei der Behandlung verwendeten Stoffe behandelt, das Bad danach ablässt und das Material mit gereinigtem Wasser spült, und
5) das so erhaltene Material mit einem Bad aus gereinigtem Wasser, das einen durch Zusatz einer organischen Säure erhaltenen pH von ungefähr 3 aufweist, unter Umlauf genügend lange behandelt, um gleichmässige Verteilung der Säure zu erzielen, und das Material dann gegebenenfalls entweder direkt färbt oder entwässert und über Säure trocknet, wobei das in dem Verfahren verwendete gereinigte Wasser eine Härte unter 15° französischer Härte aufweist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als wasserlösliches Metallsalz ein Kupfersalz verwendet wird.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als wasserlösliches Salz Kupfersulfat verwendet wird.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als organische Säure Essigsäure, Ameisensäure oder Zitronensäure verwendet wird.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Oxydationsmittel Wasserstoffperoxyd verwendet wird.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als organische Base ein C2-C4-Alkanolamin verwendet wird.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man die organische Base unter Monoäthanolamin, Diäthanolamin und Triäthanolamin auswählt.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Reduktionsmittel ein Dithionit verwendet wird.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein unter Ferrosalzen, Aluminiumsalzen, Titansalzen und Chromsalzen ausgewähltes wasserlösliches Salz verwendet wird.
EP83106432A 1982-07-07 1983-07-01 Verfahren zur Antifilzbehandlung von Keratinfasern, eine basische, durch ein Metallsalz katalysierte Oxydation beinhaltend und auf diese Weise erhaltene Fasern Expired EP0098544B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83106432T ATE26136T1 (de) 1982-07-07 1983-07-01 Verfahren zur antifilzbehandlung von keratinfasern, eine basische, durch ein metallsalz katalysierte oxydation beinhaltend und auf diese weise erhaltene fasern.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8211950A FR2529921A1 (fr) 1982-07-07 1982-07-07 Procede de traitement anti-feutrage de fibres keratiniques, comprenant une oxydation basique catalysee par un sel metallique, et fibres ainsi obtenues
FR8211950 1982-07-07

Publications (3)

Publication Number Publication Date
EP0098544A2 EP0098544A2 (de) 1984-01-18
EP0098544A3 EP0098544A3 (en) 1984-03-07
EP0098544B1 true EP0098544B1 (de) 1987-03-25

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EP83106432A Expired EP0098544B1 (de) 1982-07-07 1983-07-01 Verfahren zur Antifilzbehandlung von Keratinfasern, eine basische, durch ein Metallsalz katalysierte Oxydation beinhaltend und auf diese Weise erhaltene Fasern

Country Status (7)

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US (1) US4492585A (de)
EP (1) EP0098544B1 (de)
JP (1) JPS5976968A (de)
AT (1) ATE26136T1 (de)
CA (1) CA1193055A (de)
DE (1) DE3370498D1 (de)
FR (1) FR2529921A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (ja) * 2013-02-19 2016-12-27 丸三綿業株式会社 カシミヤ原毛繊維の洗浄方法
CN113005772A (zh) * 2021-02-21 2021-06-22 浙江理工大学 用于天然彩色棉产品的功能维护剂及其应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL67693C (de) * 1946-07-24
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 (fr) * 1965-05-07 1966-04-15 Prec Processes Textiles Ltd Procédé continu pour rendre la laine résistante au rétrécissement à l'aide d'un agent oxydant exempt d'halogènes
US3632295A (en) * 1969-04-29 1972-01-04 Gillette Co Method of bleaching hair or wool

Also Published As

Publication number Publication date
JPS5976968A (ja) 1984-05-02
US4492585A (en) 1985-01-08
ATE26136T1 (de) 1987-04-15
CA1193055A (fr) 1985-09-10
EP0098544A3 (en) 1984-03-07
DE3370498D1 (en) 1987-04-30
EP0098544A2 (de) 1984-01-18
FR2529921B1 (de) 1985-05-17
FR2529921A1 (fr) 1984-01-13

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