EP0654557A1 - Process for bleaching indigo-dyed denim articles - Google Patents
Process for bleaching indigo-dyed denim articles Download PDFInfo
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- EP0654557A1 EP0654557A1 EP94890191A EP94890191A EP0654557A1 EP 0654557 A1 EP0654557 A1 EP 0654557A1 EP 94890191 A EP94890191 A EP 94890191A EP 94890191 A EP94890191 A EP 94890191A EP 0654557 A1 EP0654557 A1 EP 0654557A1
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- Prior art keywords
- bleaching
- denim
- articles
- vat
- indigo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/268—Carbohydrates or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
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- 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
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- 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
- D06P1/228—Indigo
Definitions
- the present invention relates to a method for bleaching textile articles, in particular denim articles or warp bodies consisting of indigo-dyed chain and white weft, with reducing agents.
- Denim is a weaving technique in which the warp consists of a yarn dyed with indigo continuity and the weft is made of a white yarn.
- the warp consists of a yarn dyed with indigo continuity and the weft is made of a white yarn.
- blue denim a frequently used fabric for the production of blue jeans, is a three-stranded warp body (K 2s 1 ), which mainly shows the chain dyed blue with indigo on the top of the fabric. In contrast, the predominantly white colored weft is visible on the underside of the fabric.
- the fully assembled parts are turned on the left side and prewashed or desized.
- the parts are then removed from the washing machine, turned to the right side and washed with sand-lime bricks (pumice stones) in a ratio of 1: 3 (1 kg of goods: 3 kg of stones).
- the goods are then removed from the machine, pitted and bleached with sodium hypochlorite (depending on the desired shade) (Peter, M .; Ruette, H.K., Fundamentals of Textile Finishing, 13th ed., Deutscher rachverlag 1989, pages 80-81).
- indigo dyes can be described mostly by the following formula.
- R1 to R4 structural elements
- indigoid dyes are commercially available as vat dyes, less often than pigments.
- the dyes obtainable by direct halogenation of indigo such as C.I. Vat Blue 41, C.I. Vat Blue 5, C.I. Vat Blue 37, C.I. Vat Blue 35, C.I. Vat Blue 48 or C.I. Acid Blue 74. Green tones of blue develop when, for example, chlorine is indigo or when hypochlorite is used for bleaching.
- Vat dyes are practically insoluble in water and must be made water-soluble by reduction in alkaline solution before dyeing.
- the resulting reaction product also called leuco base or vat salt, is drawn onto the substrate and can now be re-oxidized to the dye.
- Vat dyes therefore contain structural elements that make the molecule water-insoluble in oxidized form and water-soluble in reduced form, which can be obtained reversibly.
- hypochlorite So far, it has been customary to remove these vat dyes from denim articles by using hypochlorite or bleach.
- hypochlorite Based on the regulation of the Federal Minister of Agriculture and Forestry on the limitation of waste water emissions from textile finishing and treatment companies, Federal Law Gazette No. 612 of September 24, 1992, hypochlorite must be avoided, for example in accordance with Section 33a of the Water Law Act (WRG).
- WRG Water Law Act
- the content of free chlorine, calculated as Cl2 in the wastewater of these companies may not exceed 0.2 mg / l, and absorbable organically bound halogens (AOX), calculated as Cl, may not exceed 0.5 mg / l.
- AOX absorbable organically bound halogens
- the conventional production of stone-washed denim leaves considerable amounts of active chlorine in the bleaching liquor. Chlorination of the vat dyes creates organic molecules that are carried away with the wash liquors and determined as AOX in the wastewater.
- hypochlorite liquor has the further disadvantage that some vat dyes give a greenish blue when the dye molecule is chlorinated.
- the aim is to pull the dye off the indigo-dyed chain and prevent it from being drawn onto the white weft thread (dyeing).
- the color should become lighter, but the color depth should not be changed.
- AOX and active chlorine in wastewater must be prevented.
- the object of the invention is therefore to avoid the disadvantages mentioned above, to produce uniformly lightened denim articles without dyeing the white weft and the Change color depth. Chlorine and organochlorine compounds in waste water should be prevented.
- the process according to the invention consists of exposing the fabric to an aqueous bath at elevated temperatures which contains a reducing agent mixture, an alkali metal hydroxide and preferably a surface-active substance.
- the best known reducing agents used in vat dyeing of cellulose fibers are sodium dithionite, formamidine sulfinic acid (thiourea dioxide) and hydroxyacetone.
- the denim articles can be bleached, for example, in liquor ratios of 1: 1 to 1:40, preferably 1: 5 to 1: 7.
- the dyes are removed in an aqueous medium at pH values of 10-13, preferably approximately 12.5, using reducing agent mixtures and at temperatures above 50 ° C.
- Mixtures of formamidine sulfinic acid (thiourea dioxide) with carbohydrates with the general gross formula C n H 2n O n are suitable as reducing agent mixtures.
- Suitable carbohydrates are, for example, monosaccharides, disaccharides, oligosaccharides and polysaccharides, for example glucose, sucrose, starch, molasses or pectin. From the group of these reducing agents, sucrose is preferred. It is of course also possible to use mixtures of several carbohydrates as the second component of the combination to be used according to the invention, for example mixtures of sucrose and glucose.
- the weight ratio of formamidine sulfinic acid to the second component can advantageously be 80:20 to 99: 1.
- the pH is preferably adjusted by adding NaOH.
- Other bases such as KOH can be used.
- the denim articles After being stoned, the denim articles are placed in fresh water and the temperature is raised to over 50 ° C. From 75 ° C, a prepared solution consisting of formamidine sulfinic acid and second component, sodium hydroxide solution and textile auxiliaries (dispersant, wetting agent) is dosed into the washing machine. With the movement of the liquor and the articles, the vat dyes are made soluble and detached from the fiber (indigo-dyed chain). The bleaching time is 1 to 30 minutes, preferably 15 minutes. The reducing agent mixtures are used in amounts of 0.5 to 10%, preferably 2 or 4%, depending on the desired brightness. The liquor is drained after this treatment and the denim articles are rinsed with water at 40 ° C. The second rinsing bath is concentrated 2 g / l acetic acid. and 1 g / l of hydrogen peroxide were added. The denim articles are then spun and dried.
- a prepared solution consisting of formamidine sulfinic acid and second component,
- the process according to the invention can of course also be carried out in the presence of customary textile auxiliaries such as wetting agents, dispersants, surfactants etc.
- the advantages of the method according to the invention are that the denim articles can be bleached very reproducibly.
- the dye is from the indigo-dyed chain reductively replaced.
- the concentration of the reducing agent formamidine sulfinic acid can be selected in such a way that the white weft is prevented from being colored. Contrary to the usual dyeing, one part of the fabric (warp) is decolorized in a controlled manner without the other part of the fabric (weft) being stained at the same time.
- the wastewater is free of chlorine and AOX.
- the waste water pollution is significantly lower than when using sodium hypochlorite.
- the vat dye can be recovered from the wastewater with minimal means.
- the bleached denim articles had an average whiteness of 19.4 (filter R 457) and a yellowness index of -66.5. The chain is clearly lightened and the weft is pure white.
- the bleaching liquor has a COD of 7280 mg O2 / l and is free of absorbable organic halogens (AOX).
- the bleached denim articles had a whiteness of 43.7 (raw material 8.8), measured with a whiteness measuring device (filter R 457), and a yellowness index of -24.0 (raw material -98.5).
- This brightness is comparable to a bleached denim article that has been treated with sodium hypochlorite.
- the analysis of the waste water after bleaching with sodium hypochlorite showed a COD value of 18600 mg O2 / l.
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Bleiche von Textilartikeln, insbesondere Denim-Artikeln bzw. Kettkörpern bestehend aus Indigo-gefärbter Kette und weißem Schuß, mit Reduktionsmitteln.The present invention relates to a method for bleaching textile articles, in particular denim articles or warp bodies consisting of indigo-dyed chain and white weft, with reducing agents.
Inspiriert von moderner Verfahrenstechnik und angetrieben vom Willen zu modegerechter Textilgestaltung durch Waschen, Bleichen und Färben hat es nie an Versuchen zur Variation der Denim-Artikel gefehlt. Denim ist eine Webtechnik, bei der die Kette aus einem mit Indigo-Kontinue-gefärbten Garn und der Schuß aus einem weißen Garn besteht. Blue Denim, ein häufig eingesetztes Gewebe für die Erzeugung von Blue Jeans, ist zum Beispiel ein dreibindiger Kettkörper (K
Es wurde deshalb von Industriewäschern immer wieder versucht, durch ausgefallene Technologien eine Ätzung in mechanischer (stone wash-) oder in chemischer (snow wash-) Form vorzunehmen. Ein typisches Verfahren von Industriewäschereien zur Herstellung modischer Jeans-Artikel im Stone wash-Verfahren läuft wie folgt ab:Industrial washers have therefore repeatedly tried to use mechanical technologies (stone wash) or chemical (snow wash) to etch them. A typical process used by industrial laundries to produce fashionable jeans items using the stone wash process is as follows:
Die fertig konfektionierten Teile werden auf die linke Seite gedreht und vorgewaschen bzw. entschlichtet. Die Teile werden dann aus der Waschmaschine genommen, auf die rechte Seite gedreht und mit Kalksandsteinen (Bimssteinen) im Verhältnis 1:3 (1 kg Ware:3 kg Steine) gewaschen. Die Ware wird dann aus der Maschine genommen, entsteint und mit Natriumhypochlorit (je nach gewünschter Nuance) gebleicht (Peter, M.; Ruette, H.K., Grundlagen der Textilveredlung, 13. Aufl., Deutscher rachverlag 1989, Seiten 80-81).The fully assembled parts are turned on the left side and prewashed or desized. The parts are then removed from the washing machine, turned to the right side and washed with sand-lime bricks (pumice stones) in a ratio of 1: 3 (1 kg of goods: 3 kg of stones). The goods are then removed from the machine, pitted and bleached with sodium hypochlorite (depending on the desired shade) (Peter, M .; Ruette, H.K., Fundamentals of Textile Finishing, 13th ed., Deutscher rachverlag 1989, pages 80-81).
Im Sprachgebrauch der Textilveredlung fällt diese Art der Fertigwarenaufbereitung unter den Begriff "Fully fashioned"-Ausrüstung.In the vernacular of textile finishing, this type of finished goods preparation falls under the term "fully fashioned" equipment.
Gemäß DE-A1-38 33 194 wird beim Färben von textilen Materialien, die aus Cellulosefasern bestehen oder Cellulosefasern in Mischung mit Synthesefasern enthalten, mit Küpenfarbstoffen in alkalisch-wäßrigem Medium in Anwesenheit von Reduktionsmitteln und gegebenenfalls weiterer üblicher Hilfsstoffe bei Temperaturen von beispielsweise 45-60°C gearbeitet. Anschließend stellt man die Färbungen dadurch fertig, daß man das textile Material spült, oxidiert und seift.According to DE-A1-38 33 194, when dyeing textile materials which consist of cellulose fibers or contain cellulose fibers in a mixture with synthetic fibers, with vat dyes worked in an alkaline aqueous medium in the presence of reducing agents and optionally other customary auxiliaries at temperatures of, for example, 45-60.degree. The dyeings are then finished by rinsing, oxidizing and soaping the textile material.
Das Bauprinzip der indigoiden Farbstoffe läßt sich mehrheitlich nach folgender Formel beschreiben.
D₁=D₂=NH = indigoider Farbstoff im engeren Sinn
D₁=D₂=S = thioindigoider Farbstoff
R₁ bis R₄ = StrukturelementeThe construction principle of indigo dyes can be described mostly by the following formula.
D₁ = D₂ = NH = indigoid dye in the narrower sense
D₁ = D₂ = S = thioindigoider dye
R₁ to R₄ = structural elements
Der Einbau dieser Strukturelemente R, D und CO in heterocyclische Ringe führt zu stabilen, technisch nutzbaren Farbstoffen, wie dem klassischen Indigo, das im Colour Index unter der Bezeichnung C.I. Vat Blue 1 oder C.I. Pigment Blue 66 registriert und im Handel erhältlich ist.The incorporation of these structural elements R, D and CO into heterocyclic rings leads to stable, technically usable dyes, such as the classic indigo, which is called C.I. in the Color Index. Vat Blue 1 or C.I. Pigment Blue 66 is registered and commercially available.
Die zahlreichen Vertreter indigoider Farbstoffe sind als sogenannte Küpenfarbstoffe, seltener als Pigmente, im Handel. Besonders bewährt haben sich auch die durch direkte Halogenierung von Indigo erhältlichen Farbstoffe, wie C.I. Vat Blue 41, C.I. Vat Blue 5, C.I. Vat Blue 37, C.I. Vat Blue 35, C.I. Vat Blue 48 oder C.I. Acid Blue 74. Grünstichige Blautöne entstehen, wenn zum Beispiel Indigo chloriert wird oder wenn Hypochlorit zur Bleiche verwendet wird.The numerous representatives of indigoid dyes are commercially available as vat dyes, less often than pigments. The dyes obtainable by direct halogenation of indigo, such as C.I. Vat Blue 41, C.I. Vat Blue 5, C.I. Vat Blue 37, C.I. Vat Blue 35, C.I. Vat Blue 48 or C.I. Acid Blue 74. Green tones of blue develop when, for example, chlorine is indigo or when hypochlorite is used for bleaching.
Küpenfarbstoffe sind praktisch unlöslich in Wasser und müssen vor dem Färben durch Reduktion in alkalischer Lösung wasserlöslich gemacht werden. Das entstandene Reaktionsprodukt, auch Leukobase oder Küpensalz genannt, zieht auf das Substrat auf und kann nun zum Farbstoff rückoxidiert werden. Küpenfarbstoffe enthalten also Strukturelemente, die das Molekül in oxidierter Form wasserunlöslich und in reduzierter Form, die reversibel erhalten werden kann, wasserlöslich machen.Vat dyes are practically insoluble in water and must be made water-soluble by reduction in alkaline solution before dyeing. The resulting reaction product, also called leuco base or vat salt, is drawn onto the substrate and can now be re-oxidized to the dye. Vat dyes therefore contain structural elements that make the molecule water-insoluble in oxidized form and water-soluble in reduced form, which can be obtained reversibly.
Üblich war bisher die Entfernung dieser Küpenfarbstoffe von Denim-Artikeln durch Verwendung von Hypochlorit oder Bleichlauge. Aufgrund der Verordnung des Bundesministers für Land- und Forstwirtschaft über die Begrenzung von Abwasseremissionen aus Textilveredelungs- und -behandlungsbetrieben, Bundesgesetzblatt Nr. 612 vom 24. September 1992, muß z.B. gemäß § 33a Wasserrechtsgesetz (WRG) Hypochlorit vermieden werden. Der Gehalt an freiem Chlor, berechnet als Cl₂, im Abwasser dieser Betriebe darf 0,2 mg/l, und absorbierbare organisch gebundene Halogene (AOX), berechnet als Cl, dürfen 0,5 mg/l nicht überschreiten. Bei der konventionellen Erzeugung von stone-washed Denim werden beträchtliche Mengen an Aktivchlor in der Bleichflotte zurückgelassen. Durch Chlorierung der Küpenfarbstoffe entstehen organische Moleküle, die mit den Waschflotten ausgetragen und im Abwasser als AOX bestimmt werden.So far, it has been customary to remove these vat dyes from denim articles by using hypochlorite or bleach. Based on the regulation of the Federal Minister of Agriculture and Forestry on the limitation of waste water emissions from textile finishing and treatment companies, Federal Law Gazette No. 612 of September 24, 1992, hypochlorite must be avoided, for example in accordance with Section 33a of the Water Law Act (WRG). The content of free chlorine, calculated as Cl₂, in the wastewater of these companies may not exceed 0.2 mg / l, and absorbable organically bound halogens (AOX), calculated as Cl, may not exceed 0.5 mg / l. The conventional production of stone-washed denim leaves considerable amounts of active chlorine in the bleaching liquor. Chlorination of the vat dyes creates organic molecules that are carried away with the wash liquors and determined as AOX in the wastewater.
Die Verwendung von Hypochloritlauge hat weiters den Nachteil, daß einige Küpenfarbstoffe ein grünstichiges Blau ergeben, wenn das Farbstoffmolekül chloriert wird.The use of hypochlorite liquor has the further disadvantage that some vat dyes give a greenish blue when the dye molecule is chlorinated.
Übliche, in der Textilfärbung gebräuchliche Methoden können bei der Bleiche von Denim-Artikeln nicht angewendet werden. Bei der Färbung liegt das Ziel darin, eine möglichst gleichmäßige Färbung und ein egales Aufziehen des Farbstoffes auf die Faser zu erhalten. Bisher konnte mit Reduktionsmitteln und auch Reduktionsmittelmischungen wohl der Küpenfarbstoff als Leukobase wasserlöslich gemacht werden. Der Farbstoff zieht aber gleichzeitig auf die Faser auf. Als gebräuchliche Reduktionsmittel werden Natriumdithionit, Hydroxymethansulfinsäure, Thioharnstoffdioxid (Formamidinsulfinsäure) oder auch Mischungen dieser Verbindungen beschrieben. Zu starke Reduktionsmittel können nicht eingesetzt werden, weil der Farbstoff überreduziert und zerstört werden kann (DE-A1-20 11 387). Gemäß DE-A1-38 33 194 werden weiters alpha-Hydroxycarbonylverbindungen in Betracht gezogen, um eine Überreduktion zu vermeiden.Usual methods used in textile dyeing cannot be used for bleaching denim articles. The aim of dyeing is to achieve the most uniform possible dyeing and a level drawing of the dye onto the fiber. So far, vat dye as a leuco base has probably been made water-soluble with reducing agents and also reducing agent mixtures. At the same time, the dye is drawn onto the fiber. Sodium dithionite, hydroxymethanesulfinic acid, thiourea dioxide (formamidinesulfinic acid) or mixtures of these compounds are described as common reducing agents. Too strong reducing agents cannot be used because the dye can be over-reduced and destroyed (DE-A1-20 11 387). According to DE-A1-38 33 194, alpha-hydroxycarbonyl compounds are also taken into account in order to avoid over-reduction.
Beim Bleichen von Denim-Artikeln liegt hingegen das Ziel darin, den Farbstoff von der Indigo-gefärbten Kette abzuziehen und ein Aufziehen auf den weißen Schußfaden (Färben) zu verhindern. Der Farbton soll heller werden, aber in der Farbtiefe nicht verändert werden. AOX und Aktivchlor im Abwasser müssen verhindert werden.When bleaching denim articles, on the other hand, the aim is to pull the dye off the indigo-dyed chain and prevent it from being drawn onto the white weft thread (dyeing). The color should become lighter, but the color depth should not be changed. AOX and active chlorine in wastewater must be prevented.
Aufgabe der Erfindung ist es daher, die vorab angeführten Nachteile zu vermeiden, gleichmäßig aufgehellte Denim-Artikel herzustellen, ohne den weißen Schußfaden anzufärben und die Farbtiefe zu verändern. Chlor und chlororganische Verbindungen im Abwasser sollen verhindert werden.The object of the invention is therefore to avoid the disadvantages mentioned above, to produce uniformly lightened denim articles without dyeing the white weft and the Change color depth. Chlorine and organochlorine compounds in waste water should be prevented.
Das erfindungsgemäße Verfahren besteht darin, das Gewebe bei erhöhten Temperaturen einem wäßrigen Bad auszusetzen, das eine Reduktionsmittelmischung, ein Alkalihydroxid und vorzugsweise einen oberflächenaktiven Stoff enthält. Die vorab angeführten Nachteile, wie die Bildung von Aktivchlor und absorbierbaren organischen Halogenen, eine Überreduktion der Farbstoffe und zu hohe CSB-Lasten im Abwasser, werden solcherart vermieden.The process according to the invention consists of exposing the fabric to an aqueous bath at elevated temperatures which contains a reducing agent mixture, an alkali metal hydroxide and preferably a surface-active substance. The previously mentioned disadvantages, such as the formation of active chlorine and absorbable organic halogens, an over-reduction of the dyes and excessive COD loads in the waste water, are avoided in this way.
Die bekanntesten Reduktionsmittel, die bei der Küpenfärbung von Cellulosefasern eingesetzt werden, sind Natriumdithionit, Formamidinsulfinsäure (Thioharnstoffdioxid) und Hydroxyaceton.The best known reducing agents used in vat dyeing of cellulose fibers are sodium dithionite, formamidine sulfinic acid (thiourea dioxide) and hydroxyacetone.
So ist beispielsweise aus der DE-A1-20 11 387 bekannt, bei der Küpenfärbung von Cellulosefasern enthaltenden Textilien Formamidinsulfinsäure als Reduktionsmittel zu verwenden. Wie aus dieser Patentschrift außerdem bekannt ist, kann die Reduktion der Küpenfarbstoffe zusätzlich in Gegenwart von Glucose vorgenommen werden, um zu verhindern, daß empfindliche Farbstoffe "überreduziert" werden. Die Egalität der Küpenfärbungen wird als verbesserungswürdig beschrieben.For example, it is known from DE-A1-20 11 387 to use formamidine sulfinic acid as a reducing agent in the vat dyeing of textiles containing cellulose fibers. As is also known from this patent, the reduction of the vat dyes can additionally be carried out in the presence of glucose in order to prevent sensitive dyes from being "over-reduced". The level of vat dyeing is described as in need of improvement.
In der DE-A1 38 33 194 wird die Aufgabe, textile Materialien aus Cellulosefasern mit Küpenfarbstoffen zu färben, dadurch gelöst, daß man als Reduktionsmittelmischungen Kombinationen aus den Komponenten
- A) Natriumdithionit und/oder Formamidinsulfinsäure und
- B) alpha-Hydroxycarbonylverbindungen im Gewichtsverhältnis 1:1 bis 1:15 einsetzt und die Färbung bei pH-Werten von mindestens 13 sowie bei Temperaturen oberhalb von 75°C durchführt.
- A) sodium dithionite and / or formamidine sulfinic acid and
- B) uses alpha-hydroxycarbonyl compounds in a weight ratio of 1: 1 to 1:15 and the dyeing is carried out at pH values of at least 13 and at temperatures above 75 ° C.
Überraschend wurde nun gefunden, daß die Bleiche von Denim-Artikeln mit Reduktionsmitteln durchgeführt werden kann. Die Bleiche der Denim-Artikel kann beispielsweise bei Flottenverhältnissen von 1:1 bis 1:40, vorzugsweise 1:5 bis 1:7, erfolgen.Surprisingly, it has now been found that the bleaching of denim articles can be carried out using reducing agents. The denim articles can be bleached, for example, in liquor ratios of 1: 1 to 1:40, preferably 1: 5 to 1: 7.
Erfindungsgemäß erfolgt die Entfernung der Farbstoffe im wäßrigen Medium bei pH-Werten von 10-13, vorzugsweise bei etwa 12,5, unter Verwendung von Reduktionsmittelmischungen und bei Temperaturen über 50°C. Als Reduktionsmittelmischungen kommen Mischungen von Formamidinsulfinsäure (Thioharnstoffdioxid) mit Kohlenhydraten mit der allgemeinen Bruttoformel CnH2nOn in Betracht. Geeignete Kohlenhydrate sind z.B. Monosaccharide, Disaccharide, Oligosaccharide und Polysaccharide, beispielsweise Glucose, Saccharose, Stärke, Melasse oder Pektin. Aus der Gruppe dieser Reduktionsmittel kommt vorzugsweise Saccharose in Betracht. Es ist selbstverständlich auch möglich, Mischungen mehrerer Kohlenhydrate als zweite Komponente der erfindungsgemäß einzusetzenden Kombination zu verwenden, z.B. Mischungen aus Saccharose und Glucose.According to the invention, the dyes are removed in an aqueous medium at pH values of 10-13, preferably approximately 12.5, using reducing agent mixtures and at temperatures above 50 ° C. Mixtures of formamidine sulfinic acid (thiourea dioxide) with carbohydrates with the general gross formula C n H 2n O n are suitable as reducing agent mixtures. Suitable carbohydrates are, for example, monosaccharides, disaccharides, oligosaccharides and polysaccharides, for example glucose, sucrose, starch, molasses or pectin. From the group of these reducing agents, sucrose is preferred. It is of course also possible to use mixtures of several carbohydrates as the second component of the combination to be used according to the invention, for example mixtures of sucrose and glucose.
Das Gewichtsverhältnis Formamidinsulfinsäure zur zweiten Komponente kann vorteilhaft 80:20 bis 99:1 betragen. Der pH-Wert wird vorzugsweise durch Zugabe von NaOH eingestellt. Auch andere Basen wie z.B. KOH können eingesetzt werden.The weight ratio of formamidine sulfinic acid to the second component can advantageously be 80:20 to 99: 1. The pH is preferably adjusted by adding NaOH. Other bases such as KOH can be used.
Die Denim-Artikel werden nach dem Entsteinen in frisches Wasser gegeben und die Temperatur wird auf über 50°C erhöht. Ab 75°C wird eine vorbereitete Lösung, bestehend aus Formamidinsulfinsäure und zweiter Komponente, Natronlauge und Textilhilfsmittel (Dispergator, Netzmittel), in die Waschmaschine dosiert. Unter Bewegung der Flotte und der Artikel werden die Küpenfarbstoffe löslich gemacht und von der Faser (Indigo-gefärbte Kette) abgelöst. Die Bleichzeit beträgt 1 bis 30 Minuten, vorzugsweise 15 Minuten. Die Reduktionsmittel-Mischungen werden in Mengen von 0,5 bis 10%, vorzugsweise 2 bzw. 4%, je nach gewünschter Helligkeit angewendet. Die Flotte wird nach dieser Behandlung abgelassen und die Denim-Artikel werden mit Wasser bei 40°C gespült. Dem zweiten Spülbad werden 2 g/l Essigsäure konz. und 1 g/l Wasserstoffperoxid zugefügt. Anschließend werden die Denim-Artikel geschleudert und getrocknet.After being stoned, the denim articles are placed in fresh water and the temperature is raised to over 50 ° C. From 75 ° C, a prepared solution consisting of formamidine sulfinic acid and second component, sodium hydroxide solution and textile auxiliaries (dispersant, wetting agent) is dosed into the washing machine. With the movement of the liquor and the articles, the vat dyes are made soluble and detached from the fiber (indigo-dyed chain). The bleaching time is 1 to 30 minutes, preferably 15 minutes. The reducing agent mixtures are used in amounts of 0.5 to 10%, preferably 2 or 4%, depending on the desired brightness. The liquor is drained after this treatment and the denim articles are rinsed with water at 40 ° C. The second rinsing bath is concentrated 2 g / l acetic acid. and 1 g / l of hydrogen peroxide were added. The denim articles are then spun and dried.
Das erfindungsgemäße Verfahren kann selbstverständlich auch in Anwesenheit üblicher Textilhilfsmittel wie Netzer, Dispergiermittel, Tenside usw. durchgeführt werden.The process according to the invention can of course also be carried out in the presence of customary textile auxiliaries such as wetting agents, dispersants, surfactants etc.
Die Vorteile des erfindungsgemäßen Verfahrens liegen darin, daß die Denim-Artikel sehr reproduzierbar gebleicht werden können. Der Farbstoff wird von der Indigo-gefärbten Kette reduktiv abgelöst. Die Konzentration des Reduktionsmittels Formamidinsulfinsäure kann derart gewählt werden, daß ein Anfärben des weißen Schußfadens verhindert wird. Entgegen einer üblichen Färbung wird erfindungsgemäß ein Gewebeteil (Kette) kontrolliert entfärbt, ohne daß gleichzeitig der andere Gewebeteil (Schuß) angefärbt wird. Das Abwasser ist frei von Chlor und AOX. Die Abwasserbelastung ist deutlich geringer als bei Verwendung von Natriumhypochlorit. Mit geringen Mitteln läßt sich der Küpenfarbstoff aus dem Abwasser wiedergewinnen.The advantages of the method according to the invention are that the denim articles can be bleached very reproducibly. The dye is from the indigo-dyed chain reductively replaced. The concentration of the reducing agent formamidine sulfinic acid can be selected in such a way that the white weft is prevented from being colored. Contrary to the usual dyeing, one part of the fabric (warp) is decolorized in a controlled manner without the other part of the fabric (weft) being stained at the same time. The wastewater is free of chlorine and AOX. The waste water pollution is significantly lower than when using sodium hypochlorite. The vat dye can be recovered from the wastewater with minimal means.
Folgende Beispiele sollen die Erfindung erläutern, ohne dieselbe einzuschränken:The following examples are intended to illustrate the invention without restricting it:
Ansatz der Bleichlösung:Bleaching solution approach:
In einen Behälter mit Rührwerk werden 5 l Wasser, 25°C, zugegeben, in dem unter Rühren 60 g Ätznatron, 38 g Formamidinsulfinsäure und 2 g Saccharose gelöst werden.
Durchführung der Bleiche:5 l of water, 25 ° C., are added to a container with a stirrer, in which 60 g of caustic soda, 38 g of formamidine sulfinic acid and 2 g of sucrose are dissolved with stirring.
How to do the bleaching:
4 kg stone-washed Denim-Artikel (Blue Jeans) und 20 l Wasser werden auf 75°C erwärmt. Nach Erreichen der Temperatur wird die Bleichlösung zugegeben. Nach 15 Minuten Bewegung in der Waschmaschine wird die Flotte abgelassen und bei ca. 40°C werden die Denim-Artikel gespült. Dem zweiten Spülbad werden 2 g/l Essigsäure und 1 g/l Wasserstoffperoxid 35%ig hinzugefügt. Anschließend werden die Artikel geschleudert und getrocknet. Der pH-Wert der Flotte ist von 13 auf 12,3 abgesunken. Am Rohstoff wurde ein Weißgehalt (Filter R 457) von 8,8 und ein Gelbwert von -98,5 gemessen. Die gebleichten Denim-Artikel hatten einen durchschnittlichen Weißgrad von 19,4 (Filter R 457) und einen Gelbwert von -66,5. Die Kette ist deutlich aufgehellt und der Schuß ist rein weiß. Die Bleichflotte hat einen CSB-Wert von 7280 mg O₂/l und ist frei von absorbierbaren organischen Halogenen (AOX).4 kg of stone-washed denim articles (blue jeans) and 20 l of water are heated to 75 ° C. After the temperature has been reached, the bleaching solution is added. After 15 minutes of movement in the washing machine, the liquor is drained off and the denim articles are rinsed at approx. 40 ° C. 2 g / l acetic acid and 1 g / l 35% hydrogen peroxide are added to the second rinsing bath. The articles are then spun and dried. The pH of the fleet has dropped from 13 to 12.3. A white content (filter R 457) of 8.8 and a yellowness index of -98.5 were measured on the raw material. The bleached denim articles had an average whiteness of 19.4 (filter R 457) and a yellowness index of -66.5. The chain is clearly lightened and the weft is pure white. The bleaching liquor has a COD of 7280 mg O₂ / l and is free of absorbable organic halogens (AOX).
Ansatz der Bleichlösung:Bleaching solution approach:
In ca. 7 l Wasser werden 720 g Natronlauge 50%ig unter Rühren und 228 g Formamidinsulfinsäure und 12 g Saccharose aufgelöst.
Durchführung der Bleiche:720 g of 50% strength sodium hydroxide solution and 228 g of formamidine sulfinic acid and 12 g of sucrose are dissolved in about 7 l of water.
How to do the bleaching:
6 kg stone-washed Denim-Artikel und 30 l Wasser werden auf 80°C erwärmt. Nach Zugabe der Bleichlösung und 15 Minuten Bewegung in der Waschmaschine wird die Flotte abgelassen. Aus der Flotte wird durch Zugabe von Säure und Wasserstoffperoxid der Küpenfarbstoff in die wasserunlösliche Form gebracht und durch Filtration wiedergewonnen. Die Flotte hat eine hellgelbe Farbe und einen CSB-Wert von 5000 mg O₂/l. AOX ist nicht nachweisbar. Die Denim-Artikel werden wie im Beispiel 1 gewaschen, gespült und getrocknet.6 kg of stone-washed denim and 30 l of water are heated to 80 ° C. After adding the bleaching solution and 15 minutes of movement in the washing machine, the liquor is drained off. The vat dye is brought into the water-insoluble form from the liquor by adding acid and hydrogen peroxide and recovered by filtration. The fleet has a light yellow color and a COD value of 5000 mg O₂ / l. AOX is undetectable. The denim articles are washed, rinsed and dried as in Example 1.
Die gebleichten Denim-Artikel hatten einen Weißgrad von 43,7 (Rohstoff 8,8), gemessen mit einem Weißgrad-Meßgerät (Filter R 457), und einen Gelbwert von -24,0 (Rohstoff -98,5).The bleached denim articles had a whiteness of 43.7 (raw material 8.8), measured with a whiteness measuring device (filter R 457), and a yellowness index of -24.0 (raw material -98.5).
Diese Helligkeit ist vergleichbar mit einem aebleichten Denim-Artikel, der mit Natriumhypochlorit behandelt wurde. Vergleichend ergab die Analyse des Abwassers nach einer Bleiche mit Natriumhypochlorit einen CSB-Wert von 18600 mg O₂/l.This brightness is comparable to a bleached denim article that has been treated with sodium hypochlorite. In comparison, the analysis of the waste water after bleaching with sodium hypochlorite showed a COD value of 18600 mg O₂ / l.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT2378/93 | 1993-11-23 | ||
| AT0237893A AT401274B (en) | 1993-11-23 | 1993-11-23 | METHOD FOR BLEACHING TEXTILE ARTICLES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0654557A1 true EP0654557A1 (en) | 1995-05-24 |
| EP0654557B1 EP0654557B1 (en) | 1997-03-12 |
Family
ID=3533281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94890191A Expired - Lifetime EP0654557B1 (en) | 1993-11-23 | 1994-11-22 | Process for bleaching indigo-dyed denim articles |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0654557B1 (en) |
| AT (2) | AT401274B (en) |
| DE (1) | DE59402052D1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19606620A1 (en) * | 1996-02-22 | 1997-08-28 | Henkel Kgaa | Reductive bleach |
| WO1998039512A1 (en) * | 1997-03-05 | 1998-09-11 | Basf Aktiengesellschaft | Method for bleaching dyed fabric |
| CZ299860B6 (en) * | 2003-09-02 | 2008-12-17 | Method of removing chlorine from washing bath | |
| DE102014207727A1 (en) | 2014-04-24 | 2015-10-29 | Cht R. Beitlich Gmbh | Process for lightening dyed textiles |
| EP3529282B1 (en) | 2016-10-19 | 2020-09-23 | Re:NewCell AB | Recycling of cellulosic textiles |
| EP4053328A1 (en) | 2021-03-02 | 2022-09-07 | CHT Germany GmbH | Combined bleaching treatment for textiles |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019081290A1 (en) * | 2017-10-25 | 2019-05-02 | CHT Germany GmbH | Method for removing manganese oxide deposits from textile surfaces |
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| DE2165154A1 (en) * | 1971-12-28 | 1973-07-26 | Peroxid Chemie Gmbh | PROCESS FOR PRE-TREATMENT AND BLEACHING OF TEXTILE MATERIAL |
| DE3113732A1 (en) * | 1981-04-04 | 1982-10-21 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRINTING SYNTHESIS FIBERS |
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| EP0583745A1 (en) * | 1992-08-18 | 1994-02-23 | Hoechst Aktiengesellschaft | Process for dyeing cellulose fibers with sulfur dyes |
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| SU676662A1 (en) * | 1976-04-05 | 1979-07-30 | Уральский филиал Всесоюзного научно-исследовательского и проектного института химической промышленности | "diola" bleaching composition |
| JPS61195199A (en) * | 1985-02-25 | 1986-08-29 | 旭電化工業株式会社 | Reducing agent composition |
| JPH0196297A (en) * | 1987-10-09 | 1989-04-14 | Lion Corp | Bleaching agent composition |
| DE3831098A1 (en) * | 1988-09-13 | 1990-03-22 | Ludwig Plack | Active ingredient for a composition for decolorising, stripping off-shade dyeings and weakening the shade of dyed textiles |
| US5366510A (en) * | 1992-06-09 | 1994-11-22 | Eric Wasinger | Process for desizing and color fading garments |
| JP3225473B2 (en) * | 1993-03-12 | 2001-11-05 | 旭電化工業株式会社 | Method for producing thiourea dioxide with improved stability and flowability |
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- 1993-11-23 AT AT0237893A patent/AT401274B/en not_active IP Right Cessation
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1994
- 1994-11-22 EP EP94890191A patent/EP0654557B1/en not_active Expired - Lifetime
- 1994-11-22 AT AT94890191T patent/ATE150106T1/en not_active IP Right Cessation
- 1994-11-22 DE DE59402052T patent/DE59402052D1/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2165154A1 (en) * | 1971-12-28 | 1973-07-26 | Peroxid Chemie Gmbh | PROCESS FOR PRE-TREATMENT AND BLEACHING OF TEXTILE MATERIAL |
| DE3113732A1 (en) * | 1981-04-04 | 1982-10-21 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRINTING SYNTHESIS FIBERS |
| JPS57191382A (en) * | 1981-05-14 | 1982-11-25 | Mitsui Toatsu Chemicals | Treatment of dyed article by indanethrone vat dye |
| EP0175272A2 (en) * | 1984-09-15 | 1986-03-26 | BASF Aktiengesellschaft | Process for the bleaching of wool with reducing and oxidizing agents in one bath |
| DE3833194A1 (en) * | 1988-09-30 | 1990-04-05 | Basf Ag | METHOD FOR COLORING TEXTILE MATERIALS FROM CELLULOSE FIBERS |
| EP0364752A2 (en) * | 1988-09-30 | 1990-04-25 | BASF Aktiengesellschaft | Dyeing process for textile materials from cellulose |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19606620A1 (en) * | 1996-02-22 | 1997-08-28 | Henkel Kgaa | Reductive bleach |
| WO1997031148A1 (en) * | 1996-02-22 | 1997-08-28 | Henkel Kommanditgesellschaft Auf Aktien | Reductive bleaching agent |
| DE19606620C2 (en) * | 1996-02-22 | 1999-01-07 | Henkel Kgaa | Reductive bleaching process |
| US6133219A (en) * | 1996-02-22 | 2000-10-17 | Henkel Kommanditgesellschaft Auf Aktien | Reductive bleaching agent |
| WO1998039512A1 (en) * | 1997-03-05 | 1998-09-11 | Basf Aktiengesellschaft | Method for bleaching dyed fabric |
| CZ299860B6 (en) * | 2003-09-02 | 2008-12-17 | Method of removing chlorine from washing bath | |
| DE102014207727A1 (en) | 2014-04-24 | 2015-10-29 | Cht R. Beitlich Gmbh | Process for lightening dyed textiles |
| EP3529282B1 (en) | 2016-10-19 | 2020-09-23 | Re:NewCell AB | Recycling of cellulosic textiles |
| US11618978B2 (en) | 2016-10-19 | 2023-04-04 | Re:Newcell Ab | Recycling of cellulosic textiles |
| US11891725B2 (en) | 2016-10-19 | 2024-02-06 | Re:Newcell Ab | Recycling of cellulosic textiles |
| EP4053328A1 (en) | 2021-03-02 | 2022-09-07 | CHT Germany GmbH | Combined bleaching treatment for textiles |
| WO2022184584A1 (en) | 2021-03-02 | 2022-09-09 | CHT Germany GmbH | Combined bleaching treatment for textiles |
Also Published As
| Publication number | Publication date |
|---|---|
| ATA237893A (en) | 1995-12-15 |
| AT401274B (en) | 1996-07-25 |
| EP0654557B1 (en) | 1997-03-12 |
| ATE150106T1 (en) | 1997-03-15 |
| DE59402052D1 (en) | 1997-04-17 |
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