WO1998039512A1 - Method for bleaching dyed fabric - Google Patents

Method for bleaching dyed fabric Download PDF

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Publication number
WO1998039512A1
WO1998039512A1 PCT/EP1998/001160 EP9801160W WO9839512A1 WO 1998039512 A1 WO1998039512 A1 WO 1998039512A1 EP 9801160 W EP9801160 W EP 9801160W WO 9839512 A1 WO9839512 A1 WO 9839512A1
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WO
WIPO (PCT)
Prior art keywords
acid
hydroxyalkanesulfinic
fabric
dye
tissue
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Application number
PCT/EP1998/001160
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German (de)
French (fr)
Inventor
Rudolf KRÜGER
Franz SÜTSCH
Eberhard Beckmann
Original Assignee
Basf Aktiengesellschaft
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Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU68255/98A priority Critical patent/AU6825598A/en
Publication of WO1998039512A1 publication Critical patent/WO1998039512A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/155—Locally discharging the dyes with reductants
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/621—Compounds without nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/151—Locally discharging the dyes with acids or bases
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo

Definitions

  • the invention relates to a process for lightening or for partially decolorizing tissue dyed with vat dye, the tissue being treated with hydroxyalkanesulfinic acid having 2 to 6 carbon atoms.
  • Vat dyeing is the conversion of certain water-insoluble dyes (vat dyes) by reduction (coupling) in alkaline solution into a water-soluble hydro or leuco compound, the anion of which has sufficient affinity for the fiber, for example cotton fiber or chemical fiber from regenerated cellulose (rayon), owns.
  • the dye is formed directly on the fiber in the finest distribution and thus guarantees a high degree of fastness to washing and light.
  • the yarns are then woven on looms, the threads running parallel to the bar in the longitudinal direction in the fabric being called warps or warp threads and the threads crossing at right angles being called wefts.
  • a coarse cotton fabric which is usually dyed with the vat dye indigo, is generally used for the production of hard-wearing workwear and nowadays in particular for the production of blue jeans.
  • the warp threads are dyed before weaving and the weft remains colorless.
  • the garment is partially decolored again.
  • only exposed areas of the garment should be decolored and less, for example, the seams.
  • the partial subsequent removal of dye can be done, for example, mechanically by washing out in the presence of pumice, enzymatically by partially destroying the cellulose or chemically by changing or destroying the dye (stripping).
  • the chemical change of the dye generally takes place under reductive and the destruction under oxidative conditions.
  • the following problems can generally arise:
  • vat dye detached from the chain should not bleed onto the colorless weft threads.
  • stain what is likely to occur under reductive conditions, for example in the presence of an alkaline glucose solution.
  • stripping agents are usually added to the washing liquor, which are intended to prevent or avoid staining by the dissolved dye, since the dissolved dye generally has a greater affinity for the stripping agent than for the fiber.
  • the chosen reducing agent is for the desired one
  • sodium dithionite is used as the reducing agent (hydrosulfite vat).
  • Very strong reducing agents such as sodium dithionite or thiourea dioxide emit, for example, the vat dye indigo well-behaved and complete, so that easily the entire dye z. B. deducted during washing, ie removed.
  • Weak reducing agents such as glucose or hydroxyacetone, require a relatively high working temperature and, for example, a relatively large amount of caustic alkali (sodium or potassium hydroxide). The exposure time is also relatively long.
  • Organic reducing agents such as. B.
  • glucose are no longer desirable because of their high chemical oxygen demand (COD value) in the wastewater and the former dye destruction by means of permanganate or hypochlorite is no longer used for environmental reasons (heavy metal or high value of adsorbable organic halogen compounds, AOX value) .
  • the object of the present invention is to find a process for partially decolorizing (lightening) tissue dyed with vat dyes, in which the disadvantages described are avoided or reduced and in which an optimal color contrast (wash down) is achieved relatively safely, quickly and in an environmentally compatible manner becomes.
  • Dyeing in the sense of the present invention also means pigmentation.
  • the object of the present invention is to provide a method in which the dye is largely removed from the textile in a non-uniform form without staining the weft.
  • the present invention therefore relates to a process for the partial decoloration of tissue stained with vat dye, the tissue being treated with hydroxyalkanesulfinic acid having 2 to 6, preferably having 2 to 3, carbon atoms, in particular hydroxyethanesulfinic acid. It is preferred here if the hydroxyalkanesulfinic acid in a mixture with hydroxyalkanesulfonic acid with 2 to 6, preferably with 2 to 3, in particular with hydroxyethanesulfonic acid, especially in a ratio of hydroxyalkanesulfinic acid with hydroxyalkanesulfonic acid of about 3: 1 to about 1: 3, in particular of approximately 1: 1.
  • the hydroxyalkanesulfonic acid can also be separated from the hydroxyalkanesulfinic acid (see below).
  • Fabric according to the present invention is understood to mean cellulose-containing fabric made from natural cellulose-containing material, such as cotton, linen or hemp, or from regenerated cellulose-containing material, such as modal fibers or rayon wool (viscose rayon).
  • the fabric is additionally and preferably simultaneously treated with a stripping agent, in particular with polyvinylpyrrolidone, since this primarily prevents the colorless weft from being colored by the dye which has gone into solution.
  • a stripping agent in particular with polyvinylpyrrolidone, since this primarily prevents the colorless weft from being colored by the dye which has gone into solution.
  • the ratio of hydroxyalkanesulfinic acid and stripping agent is advantageously about 20: 1 to about 5: 1, preferably about 9: 1.
  • the process according to the invention is carried out at elevated temperature, preferably approximately 40-100 ° C., in particular approximately 60-100 ° C., especially approximately 75-80 ° C. It is preferred here if the process is carried out under alkaline conditions, preferably at a pH of approximately 10.2-11.3, in particular of 10.8-11.1.
  • the partial decolorization of the fabric is generally controlled either by increasing the temperature or by the amount of alkali.
  • alkali and hydroxyalkanesulfinic acid in general or in the embodiments described in more detail above, are initially introduced together with the fabric to be partially decolorized, for example at room temperature, and the decolorization is controlled by increasing the temperature in the above-mentioned range ("all-in process"").
  • the hydroxyalkanesulfinic acid is prepared by generally known methods, for example by reacting sodium dithionite with an aldehyde, e.g. B. with acetaldehyde to produce the hydroxyethanesulfinic acid. This creates a mixture of hydroxyalkanesulfinic acid and hydroxyalkanesulfonic acid from which the hydroxyalkanesulfonic acid can be separated.
  • the hydroxyalkanesulfinic acid, especially the hydroxyethanesulfinic acid is preferably in liquid form, since this enables automatic process control of the process.
  • the liquid form of hydroxyethanesulfinic acid is also stable on storage as a mixture with hydroxyethanesulfonic acid, which is particularly advantageous.
  • vat dyes are, for example, indigo dyes such. B. indigo, dibromoindigo, indigoocamine, tetrabromoindigo, tetrachloroindigo or thioindigo; anthrachinoid dyes, such as. B.
  • Indanthrene Blue BC Indanthrene Brown NG, Indanthrene Brilliant Green FFB, Indanthrene Brilliant Orange GK, Indanthrene Brilliant Orange GR, Indanthrene Brilliant Orange RK, Indanthrene Brilliant Pink R, Indanthrene Brilliant Violet R Extra, Indanthrene Dark Blue BOA, Indanthrene Olive Green M G, Indanthrene Olive Green G, Indanthrene , Indanthrene Red RK, Indanthrene Red FBB or Indanthrene Red Violet RH; or sulfur dyes, such as. B. sulfur black T.
  • indigo dyes in particular indigo, are preferred.
  • the hydroxyalkanesulfinic acid and in particular the hydroxyethanesulfinic acid alone or in the embodiments described in more detail above are suitable for the process according to the invention in an advantageous manner, above all because their reactivity lies between the weak reducing agents, such as glucose or hydroxyacetone, and the strong reducing agents, such as hydrogen sulfite or thiourea dioxide.
  • the dyed fabric in particular under the conditions according to the invention, is generally unevenly decolored up to approximately 80-90% and the colorless weft remains essentially uncolored.
  • the so-called "wash down" effect can consequently be achieved particularly well, simply and economically.
  • the method according to the invention is particularly suitable for use in jeans laundry.
  • the air in the drum washing machine (approx. 150 l) loses its oxygen content and the pants take on the yellow color of the leuco indigo. After a linking time of approx. 20 minutes, the treatment bath is drained off. The trousers are rinsed with cold water, removing any residual hydrogen peroxide (30% by volume) can be added using 1 ml per liter of rinse water. After spinning and drying, the pants have the desired high-contrast wash-down look.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)

Abstract

The invention relates to a method for partially discolouring vat-dyed fabric, wherein said fabric is treated with hydroxyalcansulphinic acid with 2-6 carbon atoms.

Description

Verfahren zum Aufhellen von gefärbtem Gewebe Process for lightening colored tissue
Die Erfindung betrifft ein Verfahren zum Aufhellen bzw. zur teilweisen Entfärbung von mit Küpenfarbstoff gefärbtem Gewebe, wobei das Gewebe mit Hydroxyalkansulfinsäure mit 2 bis 6 Kohlenstoffatomen behandelt wird.The invention relates to a process for lightening or for partially decolorizing tissue dyed with vat dye, the tissue being treated with hydroxyalkanesulfinic acid having 2 to 6 carbon atoms.
Unter Küpenfärberei versteht man die Überfuhrung bestimmter, in Wasser unlöslicher Farbstoffe (Küpenfarbstoffe) durch Reduktion (Verküpung) in alkalischer Lösung in eine wasserlösliche Hydro- oder Leukoverbindung, deren Anion eine ausreichende Affinität zur Faser, beispielsweise Baumwollfaser oder Chemiefaser aus regenerierter Cellulose (Reyon), besitzt. Bei der Reoxidation der Leukoverbindung, beispielsweise durch "Verhängen an der Luft" entsteht der Farbstoff direkt auf der Faser in feinster Verteilung und garantiert somit eine hochgradige Wasch- und Lichtechtheit. Anschließend werden auf Webstühlen die Garne verwebt, wobei die im Gewebe in Längsrichtung parallel zur Leiste verlaufenden Fäden Kette bzw. Kettfäden oder Kettgarn genannt werden und die rechtwinklig kreuzenden Fäden Schußfäden.Vat dyeing is the conversion of certain water-insoluble dyes (vat dyes) by reduction (coupling) in alkaline solution into a water-soluble hydro or leuco compound, the anion of which has sufficient affinity for the fiber, for example cotton fiber or chemical fiber from regenerated cellulose (rayon), owns. During the reoxidation of the leuco compound, for example by "hanging in the air", the dye is formed directly on the fiber in the finest distribution and thus guarantees a high degree of fastness to washing and light. The yarns are then woven on looms, the threads running parallel to the bar in the longitudinal direction in the fabric being called warps or warp threads and the threads crossing at right angles being called wefts.
Für die Herstellung von strapazierfähiger Arbeitskleidung und heutzutage insbesondere für die Herstellung von Blue Jeans wird im allgemeinen ein grobes Baumwollgewebe (Denim) verwendet, das üblicherweise mit dem Küpenfarbstoff Indigo gefärbt wird. Um das typische Aussehen einer Blue Jeans zu erreichen, werden im allgemeinen vor dem Weben nur die Kettfäden eingefärbt und der Schuß bleibt farblos. Nach dem Weben und der Konfektionierung wird es gelegentlich gewünscht, daß das Kleidungsstück wieder teilweise entfärbt wird. Hierbei sollen lediglich exponierte Stellen des Kleidungsstückes entfärbt werden und weniger beispielsweise die Nähte. Die teilweise nachträgliche Entfernung von Farbstoff kann beispielsweise mechanisch durch Auswaschen in Anwesenheit von Bimsstein, enzymatisch durch die teilweise Zerstörung der Cellulose oder chemisch durch Veränderung oder Zerstörung des Farbstoffes (Abziehen) erfolgen. Die chemische Veränderung des Farbstoffes erfolgt im allgemeinen unter reduktiven und die Zerstörung unter oxidativen Bedingungen. Hierbei können abhängig von der jeweiligen Methode im allgemeinen folgende Probleme auftreten:A coarse cotton fabric (denim), which is usually dyed with the vat dye indigo, is generally used for the production of hard-wearing workwear and nowadays in particular for the production of blue jeans. In order to achieve the typical appearance of blue jeans, only the warp threads are dyed before weaving and the weft remains colorless. After weaving and making up, it is occasionally desired that the garment is partially decolored again. Here, only exposed areas of the garment should be decolored and less, for example, the seams. The partial subsequent removal of dye can be done, for example, mechanically by washing out in the presence of pumice, enzymatically by partially destroying the cellulose or chemically by changing or destroying the dye (stripping). The chemical change of the dye generally takes place under reductive and the destruction under oxidative conditions. Depending on the method used, the following problems can generally arise:
1. Ein guter Farbkontrast zwischen hellen und dunklen Bereichen ("wash down") wird im allgemeinen nur erreicht, wenn bereits bei der Garnfärbung auf eine sehr gute Ringfärbung, d. h. geringe Durchfärbung, geachtet wird.1. A good color contrast between light and dark areas ("wash down") is generally only achieved if a very good ring coloration, ie. H. little discoloration is observed.
2. Für die konfektionierten Textilien ist eine möglichst kurze Waschzeit erwünscht, was jedoch im allgemeinen aufgrund der schweren Entfern- barkeit beispielsweise des Indigos schlecht einzuhalten ist.2. The shortest possible washing time is desired for the ready-made textiles, but this is generally difficult to maintain due to the difficulty in removing, for example, the indigo.
3. Der von der Kette abgelöste Küpenfarbstoff soll die farblosen Schußfäden nicht anbluten, d. h. anfärben, was gerne unter reduktiven Bedin- gungen, beispielsweise in Anwesenheit von alkalischer Glukoselösung, eintritt. Daher gibt man der Waschflotte üblicherweise sogenannte Abziehmittel dazu, die das Anfärben durch den gelösten Farbstoff verhindern bzw. vermeiden sollen, da der gelöste Farbstoff im allgemeinen zu dem Abziehmittel eine größere Affinität hat als zu der Faser. Des weiteren ist das gewählte Reduktionsmittel für den gewünschten3. The vat dye detached from the chain should not bleed onto the colorless weft threads. H. stain what is likely to occur under reductive conditions, for example in the presence of an alkaline glucose solution. For this reason, so-called stripping agents are usually added to the washing liquor, which are intended to prevent or avoid staining by the dissolved dye, since the dissolved dye generally has a greater affinity for the stripping agent than for the fiber. Furthermore, the chosen reducing agent is for the desired one
Farbkontrast von Bedeutung.Color contrast important.
Im allgemeinen wird als Reduktionsmittel Natriumdithionit verwendet (Hydrosulfitküpe). Sehr starke Reduktionsmittel wie Natriumdithionit oder auch Thioharnstoffdioxid verküpen beispielsweise den Küpenfarbstoff Indigo schlag- artig und vollständig, so daß leicht der gesamte Farbstoff z. B. beim Auswaschen abgezogen, d. h. entfernt wird. Schwache Reduktionsmittel hingegen, wie Glukose oder Hydroxyaceton, verlangen eine relativ hohe Arbeitstemperatur und beispielsweise relativ viel Ätzalkali (Natrium- oder Kaliumhydroxid). Zudem ist die Einwirkungszeit relativ lang. Organische Reduktionsmittel, wie z. B. Glukose, sind wegen ihres hohen chemischen Sauerstoffbedarfs (CSB-Wert) im Abwasser nicht mehr erwünscht und die früher übliche Farbstoffzerstörung mittels Permanganat oder Hypochlorit wird aus Umweltschutzgründen (Schwermetall bzw. hoher Wert an adsorbierbaren organischen Halogenverbindungen, AOX-Wert) nicht mehr angewandt.In general, sodium dithionite is used as the reducing agent (hydrosulfite vat). Very strong reducing agents such as sodium dithionite or thiourea dioxide emit, for example, the vat dye indigo well-behaved and complete, so that easily the entire dye z. B. deducted during washing, ie removed. Weak reducing agents, however, such as glucose or hydroxyacetone, require a relatively high working temperature and, for example, a relatively large amount of caustic alkali (sodium or potassium hydroxide). The exposure time is also relatively long. Organic reducing agents, such as. B. glucose, are no longer desirable because of their high chemical oxygen demand (COD value) in the wastewater and the former dye destruction by means of permanganate or hypochlorite is no longer used for environmental reasons (heavy metal or high value of adsorbable organic halogen compounds, AOX value) .
Aufgabe der vorliegenden Erfindung ist daher, ein Verfahren zum teilweisen Entfärben (Aufhellen) von mit Küpenfarbstoffen gefärbtem Gewebe zu finden, bei dem die bezeichneten Nachteile vermieden bzw. verringert werden und bei dem ein optimaler Farbkontrast (wash down) relativ sicher, schnell und umweltverträglich erreicht wird. Unter Färben im Sinne der vorliegenden Erfindung versteht man auch das Pigmentieren. Insbesondere ist die Aufgabe der vorliegenden Erfindung, ein Verfahren bereitzustellen, bei dem der Farbstoff zum größten Teil in ungleichmäßiger Form von der Textilie abgelöst wird, ohne den Schuß anzufärben.It is therefore an object of the present invention to find a process for partially decolorizing (lightening) tissue dyed with vat dyes, in which the disadvantages described are avoided or reduced and in which an optimal color contrast (wash down) is achieved relatively safely, quickly and in an environmentally compatible manner becomes. Dyeing in the sense of the present invention also means pigmentation. In particular, the object of the present invention is to provide a method in which the dye is largely removed from the textile in a non-uniform form without staining the weft.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur teilweisen Entfärbung von mit Küpenfarbstoff gefärbtem Gewebe, wobei das Gewebe mit Hydroxyalkansulfinsäure mit 2 bis 6, vorzugsweise mit 2 bis 3 Kohlenstoffatomen, insbesondere mit Hydroxyethansulfinsäure, behandelt wird. Hierbei ist es bevorzugt, wenn die Hydroxyalkansulfinsäure in einer Mischung mit Hydroxyalkansulfonsäure mit 2 bis 6, vorzugsweise mit 2 bis 3, insbesondere mit Hydroxyethansulfonsäure, vor allem in einem Verhältnis von Hydroxyalkansulfinsäure mit Hydroxyalkansulfonsäure von ca. 3:1 bis ca. 1:3, insbesondere von ca. 1:1 vorliegt. Die Hydroxyalkansulfonsäure kann jedoch auch von der Hydroxyalkansulfinsäure abgetrennt werden (siehe unten).The present invention therefore relates to a process for the partial decoloration of tissue stained with vat dye, the tissue being treated with hydroxyalkanesulfinic acid having 2 to 6, preferably having 2 to 3, carbon atoms, in particular hydroxyethanesulfinic acid. It is preferred here if the hydroxyalkanesulfinic acid in a mixture with hydroxyalkanesulfonic acid with 2 to 6, preferably with 2 to 3, in particular with hydroxyethanesulfonic acid, especially in a ratio of hydroxyalkanesulfinic acid with hydroxyalkanesulfonic acid of about 3: 1 to about 1: 3, in particular of approximately 1: 1. The hydroxyalkanesulfonic acid can also be separated from the hydroxyalkanesulfinic acid (see below).
Unter Gewebe gemäß der vorliegenden Erfindung versteht man cellulosehalti- ges Gewebe aus natürlichem cellulosehaltigem Material, wie Baumwolle, Leinen oder Hanf, oder aus regeneriertem cellulosehaltigem Material, wie Modalfasern oder Zellwolle (Viskosereyon).Fabric according to the present invention is understood to mean cellulose-containing fabric made from natural cellulose-containing material, such as cotton, linen or hemp, or from regenerated cellulose-containing material, such as modal fibers or rayon wool (viscose rayon).
In einer weiteren vorteilhaften Ausführungsform wird das Gewebe zusätzlich und vorzugsweise gleichzeitig mit einem Abziehmittel, insbesondere mit Polyvinylpyrrolidon, behandelt, da dadurch vor allem verhindert wird, daß der farblose Schuß durch den in Lösung gegangenen Farbstoff gefärbt wird. Das Verhältnis von Hydroxyalkansulfinsäure und Abziehmittel ist hierbei vorteilhafterweise ca. 20:1 bis ca. 5: 1, vorzugsweise ca. 9:1.In a further advantageous embodiment, the fabric is additionally and preferably simultaneously treated with a stripping agent, in particular with polyvinylpyrrolidone, since this primarily prevents the colorless weft from being colored by the dye which has gone into solution. The ratio of hydroxyalkanesulfinic acid and stripping agent is advantageously about 20: 1 to about 5: 1, preferably about 9: 1.
Im allgemeinen ist es auch vorteilhaft, wenn das erfindungsgemäße Verfahren bei erhöhter Temperatur, vorzugsweise ca. 40-100°C, insbesondere ca. 60-100°C, speziell ca. 75-80 °C durchgeführt wird. Hierbei ist es bevorzugt, wenn das Verfahren unter alkalischen Bedingungen, vorzugsweise bei einem pH-Wert von ca. 10,2-11,3, insbesondere von 10,8-11,1 durchgeführt wird.In general, it is also advantageous if the process according to the invention is carried out at elevated temperature, preferably approximately 40-100 ° C., in particular approximately 60-100 ° C., especially approximately 75-80 ° C. It is preferred here if the process is carried out under alkaline conditions, preferably at a pH of approximately 10.2-11.3, in particular of 10.8-11.1.
Die Steuerung der teilweisen Entfärbung des Gewebes erfolgt im allgemeinen entweder durch Temperaturerhöhung oder durch die Alkalimenge. Bei dem erstgenannten Verfahren werden im allgemeinen Alkali- und Hydroxyalkansulfinsäure allein oder in den oben näher beschriebenen Ausführungsformen zusammen mit dem teilweise zu entfärbendem Gewebe beispielsweise bei Raumtemperatur vorgelegt und die Entfärbung durch Erhöhung der Temperatur in den oben genannten Bereich gesteuert ("All-in-Verfahren"). Bei dem zweiten Verfahren wird lediglich die Hydroxyalkansulfinsäure allein oder in den oben näher beschriebenen Ausführungsformen zusammen mit dem teilweise zu entfärbendem Gewebe vorgelegt, auf die oben genannten Temperaturbereiche erhitzt und die Entfärbung durch Zugabe von Alkalilauge (Natrium- oder Kaliumhydroxidlauge) gesteuert (Laugedosierverfahren).The partial decolorization of the fabric is generally controlled either by increasing the temperature or by the amount of alkali. In the first-mentioned process, alkali and hydroxyalkanesulfinic acid, in general or in the embodiments described in more detail above, are initially introduced together with the fabric to be partially decolorized, for example at room temperature, and the decolorization is controlled by increasing the temperature in the above-mentioned range ("all-in process""). In the second method, only the hydroxyalkanesulfinic acid is used alone or in submitted to the embodiments described in more detail above together with the fabric to be partially decolorized, heated to the above-mentioned temperature ranges and the decolorization controlled by adding alkali metal hydroxide solution (sodium or potassium hydroxide solution) (alkali dosing method).
Die Herstellung der Hydroxyalkansulfinsäure erfolgt nach allgemein bekannten Verfahren, beispielsweise durch Umsetzung von Natriumdithionit mit einem Aldehyd, z. B. mit Acetaldehyd zur Herstellung der Hydroxyethansulfinsäure. Hierbei entsteht eine Mischung von Hydroxyalkansulfinsäure und Hydroxyalkansulfonsäure, aus der die Hydroxyalkansulfonsäure abgetrennt werden kann. Die Hydroxyalkansulfinsäure, insbesondere die Hydroxyethansulfinsäure, liegt vorzugsweise in flüssiger Form vor, da dadurch eine automatische Prozessteuerung des Verfahrens möglich ist. Beispielsweise ist die flüssige Form der Hydroxyethansulfinsäure auch als Mischung mit Hy- droxyethansulfonsäure lagerstabil, was besonders vorteilhaft ist.The hydroxyalkanesulfinic acid is prepared by generally known methods, for example by reacting sodium dithionite with an aldehyde, e.g. B. with acetaldehyde to produce the hydroxyethanesulfinic acid. This creates a mixture of hydroxyalkanesulfinic acid and hydroxyalkanesulfonic acid from which the hydroxyalkanesulfonic acid can be separated. The hydroxyalkanesulfinic acid, especially the hydroxyethanesulfinic acid, is preferably in liquid form, since this enables automatic process control of the process. For example, the liquid form of hydroxyethanesulfinic acid is also stable on storage as a mixture with hydroxyethanesulfonic acid, which is particularly advantageous.
Als Küpenfarbstoffe eignen sich beispielsweise indigoide Farbstoffe, wie z. B. Indigo, Dibromindigo, Indigocamin, Tetrabromindigo, Tetrachlorindigo oder Thioindigo; anthrachinoide Farbstoffe, wie z. B. Indanthren Blau BC, Indanthren Braun NG, Indanthren Brillantgrün FFB, Indanthren Brillantorange GK, Indanthren Brillantorange GR, Indanthren Brillantorange RK, Indanthren Brillantrosa R, Indanthren Brillantviolett R extra, Indanthren Dunkelblau BOA, Indanthren Goldorange G, Indanthren Grau M, Indanthren Olivgrün B, Indanthren Rot RK, Indanthren Rot FBB oder Indanthren Rotviolett RH; oder Schwefel-Farbstoffe, wie z. B. Schwefelschwarz T. Für das erfindungsgemäße Verfahren sind vor allem indigoide Farbstoffe, insbesondere Indigo, bevorzugt.As vat dyes are, for example, indigo dyes such. B. indigo, dibromoindigo, indigoocamine, tetrabromoindigo, tetrachloroindigo or thioindigo; anthrachinoid dyes, such as. B. Indanthrene Blue BC, Indanthrene Brown NG, Indanthrene Brilliant Green FFB, Indanthrene Brilliant Orange GK, Indanthrene Brilliant Orange GR, Indanthrene Brilliant Orange RK, Indanthrene Brilliant Pink R, Indanthrene Brilliant Violet R Extra, Indanthrene Dark Blue BOA, Indanthrene Olive Green M G, Indanthrene Olive Green G, Indanthrene , Indanthrene Red RK, Indanthrene Red FBB or Indanthrene Red Violet RH; or sulfur dyes, such as. B. sulfur black T. For the process according to the invention, indigo dyes, in particular indigo, are preferred.
Die Hydroxyalkansulfinsäure und insbesondere die Hydroxyethansulfinsäure allein oder in den oben näher beschriebenen Ausfuhrungsformen eignet sich für das erfindungsgemäße Verfahren in vorteilhafter Weise, vor allem weil ihre Reaktivität zwischen den schwachen Reduktionsmitteln, wie Glukose oder Hydroxyaceton, und den starken Reduktionsmitteln, wie Hydrogensulfit oder Thioharnstoffdioxid, liegt. Hierdurch wird das gefärbte Gewebe ins- besondere unter den erfindungsgemäßen Bedingungen im allgemeinen bis zu ca. 80-90% ungleichmäßig entfärbt und der farblose Schuß bleibt im wesentlichen ungefärbt. Mit dem erfindungsgemäßen Verfahren kann folglich der sogenannte "wash down"-Effekt besonders gut, einfach und wirtschaftlich erreicht werden. Dadurch ist das erfindungsgemäße Verfahren insbesondere für den Einsatz in der Jeans-Wäscherei geeignet.The hydroxyalkanesulfinic acid and in particular the hydroxyethanesulfinic acid alone or in the embodiments described in more detail above are suitable for the process according to the invention in an advantageous manner, above all because their reactivity lies between the weak reducing agents, such as glucose or hydroxyacetone, and the strong reducing agents, such as hydrogen sulfite or thiourea dioxide. As a result, the dyed fabric, in particular under the conditions according to the invention, is generally unevenly decolored up to approximately 80-90% and the colorless weft remains essentially uncolored. With the method according to the invention, the so-called "wash down" effect can consequently be achieved particularly well, simply and economically. As a result, the method according to the invention is particularly suitable for use in jeans laundry.
Das folgende Beispiel soll die Erfindung näher erläutern, ohne sie darauf zu beschränken.The following example is intended to explain the invention in more detail without restricting it thereto.
Beispielexample
In einer Trommelwaschmaschine mit 30 kg Fassungsvermögen werden 5 kg zuvor entschlichtete und mit Enzym und/oder Bimsstein behandelte Blue- Jeans-Hosen aus indigofarbigem Denimgewebe mit 2 % fixiertem Indigo in der Kette in einem wäßrigen Behandlungsbad im Flottenverhältnis 10:1 bei 70 bis 90°C behandelt. In das wäßrige Behandlungsbad wird zuerst eine wäßrige Lösung von 3 g pro Liter Hydroxyethansulfinsäure und anschließend eine wäßrige Lösung von 0,5 g pro Liter Polyvinylpyrrolidon als Abziehmittel (backstain-inhibitor) gegeben. Durch Zugabe von Natronlauge und Puffer wird der pH-Wert auf 5,5 bis 8,5 eingestellt und damit die Ausbildung des reduktiven Milieus ausgelöst. Die in der Trommelwaschmaschine vorhandene Luft (ca. 150 1) verliert ihren Sauerstoffgehalt und die Hosen nehmen die gelbe Farbe des Leukoindigos an. Nach ca. 20 Minuten Ver- küpungszeit wird das Behandlungsbad abgelassen. Die Hosen werden mit kaltem Wasser gespült, wobei zur Entfernung von Resten des Reduktions- mittels 1 ml pro Liter Spülwasser Wasserstoffperoxid (30 Vol.-%) zugesetzt werden. Nach dem Schleudern und Trocknen haben die Hosen den gewünschten kontrastreichen wash down-Look. In a drum washing machine with a 30 kg capacity, 5 kg of desized and treated with enzyme and / or pumice stone are made of indigo-colored denim fabric with 2% fixed indigo in the chain in an aqueous treatment bath in a liquor ratio of 10: 1 at 70 to 90 ° C treated. An aqueous solution of 3 g per liter of hydroxyethanesulfinic acid and then an aqueous solution of 0.5 g per liter of polyvinylpyrrolidone is added to the aqueous treatment bath as a stripping agent (backstain inhibitor). By adding sodium hydroxide solution and buffer, the pH is adjusted to 5.5 to 8.5, thus triggering the formation of the reductive environment. The air in the drum washing machine (approx. 150 l) loses its oxygen content and the pants take on the yellow color of the leuco indigo. After a linking time of approx. 20 minutes, the treatment bath is drained off. The trousers are rinsed with cold water, removing any residual hydrogen peroxide (30% by volume) can be added using 1 ml per liter of rinse water. After spinning and drying, the pants have the desired high-contrast wash-down look.

Claims

Patentansprüche claims
1. Verfahren zur teilweisen Entfärbung von mit Küpenfarbstoff gefärbtem Gewebe, dadurch gekennzeichnet, daß das Gewebe mit Hydroxyalkansulfinsäure mit 2 bis 6 Kohlenstoffatomen behandelt wird.1. A process for the partial decoloration of tissue dyed with vat dye, characterized in that the tissue is treated with hydroxyalkanesulfinic acid having 2 to 6 carbon atoms.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Hydroxyalkansulfinsäure in einer Mischung mit Hydroxyalkansulfonsäure mit 2 bis 6 Kohlenstoffatomen vorliegt.2. The method according to claim 1, characterized in that the hydroxyalkanesulfinic acid is present in a mixture with hydroxyalkanesulfonic acid having 2 to 6 carbon atoms.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Verhältms von Hydroxyalkansulfinsäure mit Hydroxyalkansulfonsäure ca. 3: 1 bis ca. 1 :3 ist.3. The method according to claim 2, characterized in that the ratio of hydroxyalkanesulfinic acid to hydroxyalkanesulfonic acid is about 3: 1 to about 1: 3.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Gewebe zusätzlich mit einem Abziehmittel behandelt wird.4. The method according to any one of claims 1 to 3, characterized in that the fabric is additionally treated with a stripping agent.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Behandlung mit Hydroxyalkansulfinsäure und die Behandlung mit einem Ab- ziehmittel gleichzeitig erfolgen.5. The method according to claim 4, characterized in that the treatment with hydroxyalkanesulfinic acid and the treatment with a peeling agent take place simultaneously.
6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß das Verhältnis von Hydroxyalkansulfinsäure und Abziehmittel ca. 20: 1 bis ca. 5: 1 , vorzugsweise ca. 9: 1 ist.6. The method according to claim 4 or 5, characterized in that the ratio of hydroxyalkanesulfinic acid and stripping agent is about 20: 1 to about 5: 1, preferably about 9: 1.
7. Verfahren nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß das Abziehmittel Polyvinylpyrrolidon ist. 7. The method according to any one of claims 4 to 6, characterized in that the stripping agent is polyvinylpyrrolidone.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Behandlung bei ca. 40 bis 100°C durchgeführt wird.8. The method according to any one of claims 1 to 7, characterized in that the treatment is carried out at about 40 to 100 ° C.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, s daß die Behandlung bei einem pH-Wert von ca. 10,2 bis 11,3 durchgeführt wird.9. The method according to any one of claims 1 to 8, characterized in that the treatment is carried out at a pH of about 10.2 to 11.3.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die teilweise Entfärbung durch die Alkalimenge gesteuert wird. 010. The method according to claim 9, characterized in that the partial decolorization is controlled by the amount of alkali. 0
11. Verwendung von Hydroxyalkansulfinsäure zur teilweisen Entfärbung von mit Küpenfarbstoff gefärbtem Gewebe. 11. Use of hydroxyalkanesulfinic acid for the partial decoloration of tissue stained with vat dye.
PCT/EP1998/001160 1997-03-05 1998-03-02 Method for bleaching dyed fabric WO1998039512A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4227881A (en) * 1978-11-17 1980-10-14 Royce Chemical Company New process of color stripping dyed textile fabric
GB1591616A (en) * 1978-03-06 1981-06-24 Sandoz Products Ltd Process for selectively decolourising dyed substrates
EP0175272A2 (en) * 1984-09-15 1986-03-26 BASF Aktiengesellschaft Process for the bleaching of wool with reducing and oxidizing agents in one bath
EP0654557A1 (en) * 1993-11-23 1995-05-24 DEGUSSA AUSTRIA GmbH Process for bleaching indigo-dyed denim articles
WO1997035062A1 (en) * 1996-03-20 1997-09-25 Basf Aktiengesellschaft Mixtures of reducing-action sulphur compounds and organic corrosion inhibitors and their use as corrosion-inhibiting bleaching or reducing agents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1591616A (en) * 1978-03-06 1981-06-24 Sandoz Products Ltd Process for selectively decolourising dyed substrates
US4227881A (en) * 1978-11-17 1980-10-14 Royce Chemical Company New process of color stripping dyed textile fabric
EP0175272A2 (en) * 1984-09-15 1986-03-26 BASF Aktiengesellschaft Process for the bleaching of wool with reducing and oxidizing agents in one bath
EP0654557A1 (en) * 1993-11-23 1995-05-24 DEGUSSA AUSTRIA GmbH Process for bleaching indigo-dyed denim articles
WO1997035062A1 (en) * 1996-03-20 1997-09-25 Basf Aktiengesellschaft Mixtures of reducing-action sulphur compounds and organic corrosion inhibitors and their use as corrosion-inhibiting bleaching or reducing agents

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