EP3143193B1 - Method for brightening dyed textiles - Google Patents

Method for brightening dyed textiles Download PDF

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Publication number
EP3143193B1
EP3143193B1 EP15717470.7A EP15717470A EP3143193B1 EP 3143193 B1 EP3143193 B1 EP 3143193B1 EP 15717470 A EP15717470 A EP 15717470A EP 3143193 B1 EP3143193 B1 EP 3143193B1
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Prior art keywords
acid
process according
dyes
monoperoxo
dyed
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German (de)
French (fr)
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EP3143193A1 (en
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Martin Gruber
Thomas APLAS
Harald Lutz
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CHT Germany GmbH
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CHT R Beitlich GmbH
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Priority to RS20190771A priority Critical patent/RS58878B1/en
Priority to PL15717470T priority patent/PL3143193T3/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/132—Fugitive dyeing or stripping dyes with oxidants

Definitions

  • the invention relates to a process for whitening dyed textiles.
  • the classic denim, or denim, is a weave of indigo ring-dyed warp yarn and mostly undyed weft yarn.
  • the ring coloration of the warp yarn is the reason for the typical signs of wear that give the jeans their individual appearance in the course of their lives.
  • the only superficially adhering to the yarn dye (usually indigo alone or in combination with sulfur black) is gradually removed by mechanical abrasion during washing and use and the white fiber core emerges increasingly. This is increasingly the case, especially in exposed areas such as seams and wearing folds.
  • hypochlorites for example sodium hypochlorite.
  • hypochlorites for example sodium hypochlorite.
  • hypochlorites sodium hypochlorite.
  • hypochlorites sodium hypochlorite.
  • potassium permanganate For the partial bleaching of denim articles in the spray process, the use of potassium permanganate is state of the art.
  • serious disadvantages have come to light here as well in the meantime.
  • potassium permanganate exhibits high toxicity to aquatic organisms and its massive use leads to high levels of heavy metals in wastewater.
  • Chemical Prohibition Ordinance ChemVerV
  • the release of potassium permanganate in Germany requires a proof of use in order to avoid misuse for the production of explosives or drugs submissions. Similar restrictions exist in many other countries, making the purchase of potassium permanganate laborious and making stockholding more difficult.
  • an additional process step to remove the resulting manganese dioxide is also necessary in the spray treatment.
  • hypochlorite and potassium permanganate As alternatives for hypochlorite and potassium permanganate a number of approaches have been proposed, but also have serious disadvantages and could not prevail in practice.
  • vat dyes can be converted into the soluble leuco form by reducing agents, removed from the fiber, and the textile so lightened.
  • reducing agents such as glucose
  • these processes have the disadvantage that it is necessary to work at high temperatures (> 80 ° C.) and high alkalinity (pH> 11).
  • large amounts of wastewater accumulate, which also have an increased biological and chemical oxygen demand due to the high organic load.
  • reducing agents such as keto compounds, for example hydroxyacetone.
  • reducing processes for producing local bleaching effects are fundamentally unsuitable since, as in a closed washing drum, an overall reducing environment can not be produced and thus the locally produced leuco form is rapidly reoxidized by atmospheric oxygen.
  • US 3,384,596C discloses the use of peroxycarboxylic acids such as monoperoxophthalic acid and m-chloro-peroxobenzoic acid in the presence of alkaline earth salts as a bleaching agent at alkaline pH.
  • DE 34 00 950 A discloses the use of monoperoxophthalic acid magnesium salt in combination with an alkali bromide and sulfonamides in a detergent formulation also for spot bleaching in household laundry at alkaline pH.
  • peroxodisulfates as an oxygen source in combination with a transition metal catalyst.
  • peroxodisulfates are subject to the oxidizing agent same restrictions according to the ChemVerV as permanganate and therefore under this aspect not suitable as an alternative.
  • peroxodisulfate solutions as well as Fenton solutions are not suitable for achieving local effects by spray or brush application.
  • EP 0 176 124 A2 ( AT 44 763 E ) relates to the use of a suspension in water containing as bleach component a peroxycarboxylic acid derived from a dicarboxylic acid having 8 to 13 carbon atoms as a castable bleach.
  • DT 26 20 723 A1 relates to bleaching or cleaning agents, in particular with a bleaching effect at low temperatures.
  • DT 26 12 587 A1 relates to bleach preparations which comprise a water-soluble aliphatic peroxy compound and a thickener.
  • EP 0 160 342 A2 discloses liquid bleaching solutions comprising aliphatic peroxy compounds as solid, particulate, substantially water-insoluble constituents.
  • the object of the present invention is therefore to provide a method for whitening dyed textiles, which on the one hand makes it possible to lighten the textile flatly or uniformly in the desired shade, but on the other hand also locally limited, for example, by spraying or brush application in freely selectable intensity to bleach.
  • the process should provide comparable results in its lightening effect as using chlorine-based bleach or potassium permanganate, while significantly reducing potential environmental hazards and dangers. In particular, no environmentally hazardous chemicals should be used and an entry of AOX or heavy metals into the wastewater should be excluded.
  • organic peroxycarboxylic acids in particular certain linear or cyclic aliphatic or aromatic peroxocarboxylic acids or dicarboxylic acids containing hydrophobic side groups, preferably alkyl radicals having at least 5 carbon atoms, more preferably having 5 to 30 carbon atoms and more preferably having chain lengths of 6 to 10 C-atoms, have a very high whitening effect on dyed textiles.
  • indigo and indigoid dyes can be bleached under moderate conditions, so that a local treatment, for example by spraying, can be carried out simply and practically.
  • hydrophobic usually refers to the association of non-polar groups or molecules of an aqueous environment. This characterizes substances that do not mix with water and usually “roll off” on surfaces.
  • Non-polar substances such as fats, waxes, alcohols with long alkyl radicals - ie with the exception of methanol, ethanol and propanol - alkanes, alkenes etc. are hydrophobic. Dissolution of hydrophobic substances in water generally results in a so-called hydrophobic effect , and in some small, hydrophobic species, such as methane or xenon, even entropically unfavorable clathrate structures are formed. Therefore, the solubility of these substances in water is generally low.
  • Hydrophobic substances are almost always lipophilic, meaning they dissolve well in fat and oil. Surfaces with a contact angle of more than 90 ° to water are also referred to as hydrophobic.
  • Hydrophobic radicals in the context of the present invention thus comprise, in particular, a contiguous radical of at least 5 C atoms, a carbon chain, which are preferably saturated with hydrogen atoms to form an alkyl radical or an aryl radical.
  • Bleaching agents according to the invention are aromatic peroxycarboxylic acids consisting of one or more fused aromatic rings, optionally substituted with one or more further peroxycarboxylic acid groups at any position. These aromatic peroxycarboxylic acids of the invention may be further substituted with at least one functional group selected from alkyl, aryl, carboxylate, sulfonate, halide, nitro or hydroxy groups at any point on the aromatic ring system.
  • Preferred examples are: mono- or diperoxo-ortho, -meta or -para-phthalic acid, mono- or diperoxo-4-methyl-o-phthalic acid, mono- or diperoxo-1,8-naphthalenic acid.
  • the peroxycarboxylic acids may be used both in the acid form and as salts or may also be generated in situ by the addition of activated carboxylic acid derivatives (for example as anhydrides) and a hydrogen peroxide source or otherwise in the process.
  • the salts used are preferably alkali metal or alkaline earth metal salts, for example Li, Na, K, Mg or Ca salts.
  • the treatment under acidic pH conditions can be carried out particularly efficiently, although it is known to the person skilled in the art that peroxycarboxylic acids, for example peracetic acid, at a pH close to the pKa value, ie in the neutral to weakly alkaline , which have the highest bleaching efficiency.
  • peroxycarboxylic acids for example peracetic acid
  • textile fabrics are treated under acidic pH conditions.
  • the pH of the solution is in the range of pH1 to pH5, more preferably in the range of pH1.5 to pH3.5.
  • Native and synthetic thickening agents salts such as alkali metal and alkaline earth metal sulfates, phosphates and, if required, marking dyes, for example dyes, wetting agents, humectants such as glycerol, urea or dispersants or more, are used as further additives in the application liquor Auxiliary added.
  • marking dyes for example dyes, wetting agents, humectants such as glycerol, urea or dispersants or more
  • the use of dyes serves to better visual traceability of the spray course.
  • This is particularly important in practice, since the violet permanganate strongly colors the spray solution, while the spray solution according to the invention is basically colorless.
  • the pH of the solution is particularly preferably adjusted with mineral acids or organic acids.
  • very particularly preferred in this sense are low-volatile acids, that is, acids having a vapor pressure ⁇ 20 Pa at 20 ° C, such as citric acid, maleic acid, lactic acid, phthalic acid, phosphoric acid, sulfuric acid or hydrogen sulfates.
  • the colored substances are brought into contact with a solution containing all or part of the peroxycarboxylic acid or its salts by means of a spraying, dipping or brushing process.
  • textiles or textile fabrics can be brought into contact with the peroxycarboxylic acids.
  • Particularly preferred in this sense are textile fabrics made of cellulose fibers or cellulose fibers in mixture with natural or synthetic fibers, which are dyed with a wide variety of dyes.
  • these dyes are selected from the groups of vat, direct or sulfur dyes.
  • the process of the present invention is particularly suitable for textile fabrics dyed with indigo, indigoid dyes or sulfur black, as well as with combinations of these dyes.
  • bleached fabrics obtainable by a method as defined above. Jeans, as defined by these bleached fabrics, are particularly preferred.
  • the bleaching effect was determined on two different denim products each with determination of the Y values according to CIE with Datacolor International SF 600 plus CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65.
  • bleaching result preferably> 40% of the bleaching effect of a standard KMnO 4 solution has been achieved, particularly preferably> 60%, very particularly preferably> 80%.
  • denim 1 non-desized, scraping pretreatment with sandpaper
  • denim 2 desized, stonewash treatment
  • a rectangular area of 120 cm 2 was marked and covered with adhesive film at the edges against the adjacent areas. These areas were uniformly sprayed with 2 g each of an aqueous solution of 20 g / l potassium permanganate (0.38 normal) and the fabric samples were then weighed to control the amount applied.
  • the fabric samples were neutralized in a washer-extractor together with untreated denim fabric as ballast first 10 min at 50 ° C and a liquor ratio of 1: 8 with 4 g / l sodium bisulfite, then 3 times cold rinsed at a liquor ratio of 1:10 and then dried in a tumbler.
  • the Y value measured according to CIE (Datacolor International SF 600 Plus CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65) and determined from the difference in the degree of lightening with ⁇ Y.
  • MPMS monoperoxomaleic acid
  • MMPP magnesium bis-monoperoxophthalate hexahydrate
  • MPPS monoperoxophthalic acid
  • MMPP magnesium bis-monoperoxophthalate hexahydrate

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)
  • Detergent Compositions (AREA)
  • Treatment Of Fiber Materials (AREA)

Description

Gegenstand der Erfindung ist ein Verfahren zum Aufhellen von gefärbten Textilien.The invention relates to a process for whitening dyed textiles.

Seit etlichen Jahren gibt es einen anhaltenden, modischen Trend zu wash out und used-look Effekten. Dies führt zu einem steigenden Bedarf an gefärbten Textilien aus Cellulosefasern, insbesondere an mit Indigo oder anderen Farbstoffen gefärbten Denimartikeln, die in weiteren Verarbeitungsschritten durch teils mechanisch verstärkte (Stonewash) Waschprozesse, oft in Kombination mit chemischen Behandlungen, aufgehellt bzw. ganz oder stellenweise gebleicht sind.For several years, there has been a continuing, fashionable trend towards wash out and used-look effects. This leads to an increasing demand for dyed textiles made of cellulose fibers, in particular denim articles dyed with indigo or other dyes, which in further processing steps are lightened or bleached wholly or in places by partly mechanically reinforced (stonewash) washing processes, often in combination with chemical treatments ,

Der klassische Jeansstoff, oder auch Denim, ist ein Gewebe aus mit Indigo ringgefärbtem Kettgarn und meist ungefärbtem Schussgarn. Die Ringfärbung des Kettgarns ist dabei der Grund für die typischen Verschleißerscheinungen, die den Jeans im Laufe ihres Lebens ihr individuelles Aussehen verleihen. Der nur oberflächlich am Garn anhaftende Farbstoff (in der Regel Indigo allein oder in Kombination mit Schwefelschwarz) wird durch mechanischen Abrieb bei Wäsche und Gebrauch sukzessive entfernt und der weiße Faserkern tritt zunehmend hervor. Insbesondere an exponierten Stellen wie Nahtwülsten und Tragefalten ist dies verstärkt der Fall.The classic denim, or denim, is a weave of indigo ring-dyed warp yarn and mostly undyed weft yarn. The ring coloration of the warp yarn is the reason for the typical signs of wear that give the jeans their individual appearance in the course of their lives. The only superficially adhering to the yarn dye (usually indigo alone or in combination with sulfur black) is gradually removed by mechanical abrasion during washing and use and the white fiber core emerges increasingly. This is increasingly the case, especially in exposed areas such as seams and wearing folds.

Da seitens des Konsumenten ein großer Bedarf besteht, Kleidungsstücke mit Gebrauchsoptik als Neuware zu erwerben, ist die Bereitstellung des sogenannten Used- oder Vintage-Looks mittlerweile einer der kommerziell wichtigsten Modeeffekte im Freizeit-Bereich.Since there is a great need on the part of the consumer to purchase garments with utility optics as new, the provision of the so-called used or vintage look is now one of the most commercially important fashion effects in the leisure sector.

Hierzu werden Artikel aus ringgefärbten Stoffen einer abrasiven Wäsche mit Enzymen und/oder Bimssteinen unterzogen, die den Abrieb überall auf dem Artikel in der Waschtrommel erzeugt. Diese Behandlung erfolgt oftmals in Kombination mit einem zweiten Bad, das ein Bleichmittel enthält, um die Färbung zusätzlich aufzuhellen und Hell-Dunkel-Kontraste zu verstärken. Daneben wird aber auch die gezielte, lokale Aufhellung der Artikel an den entsprechend exponierten Stellen als wesentliches Mittel eingesetzt, um einer Jeans eine wirklich authentische Optik zu verleihen. Dazu wird die Denimoberfläche zuerst lokal begrenzt, beispielsweise an den Oberschenkeln und im Gesäßbereich, mechanisch durch Schleifen manuell aufgeraut. Anschließend wird gezielt an diesen Stellen mit einer Bleichlösung besprüht, die den Farbstoff mehr oder weniger, je nach gewünschter Intensität des Aufhelleffekts, zerstört. Dadurch wird ein täuschend echter Eindruck von Gebrauchs- bzw. Tragespuren auf einem neuen Denim-Artikel erzeugt.For this purpose, articles made of ring-dyed fabrics are subjected to abrasive scrubbing with enzymes and / or pumice stones, which produce abrasion everywhere on the article in the washing drum. This treatment is often done in combination with a second bath containing a bleach to the In addition to lighten the coloring and enhance light and dark contrasts. In addition, however, the targeted, local brightening of the articles in the corresponding exposed areas is used as an essential means to give a jeans a really authentic look. For this purpose, the denim surface is first locally limited, for example, on the thighs and buttocks, mechanically roughened by grinding manually. Subsequently, sprayed at these points with a bleaching solution that destroys the dye more or less, depending on the desired intensity of the whitening effect. This creates a deceptively genuine impression of signs of use or wear on a new denim article.

Es ist allgemein gebräuchlich, die Behandlung zur flächigen Aufhellung von gefärbten Textilien in einem wässrigen Bad in langer Flotte mit Hypochloriten, beispielsweise Chlorbleichlauge, durchzuführen. Mit Chlorbleichlauge steht ein einfach erhältliches, kostengünstiges und effizientes Bleichagens zur Verfügung, mit dem eine große Zahl an Farbstoffen, u.a. auch Indigo oder indigoide Farbstoffe, oxidativ entfärbt werden können. Diese Vorgehensweise hat jedoch den Nachteil, dass große Mengen an (adsorbierbaren organisch gebundenen Halogenen) AOX-belastetem Abwasser anfallen, die oftmals zur Einhaltung von behördlich verordneten Grenzwerten nachbehandelt werden müssen. Chlorbleichlauge ist sehr giftig für Wasserorganismen. Daher steht der Einsatz chlorbasierter Chemikalien bei Umwelt- und Verbraucherorganisationen stark in der Kritik. Grundsätzlich ist die Verwendung von Hypochloriten auch zur lokalen Aufhellung, beispielsweise durch Sprühen, möglich. In der Praxis findet diese Methode aber üblicherweise aufgrund der starken Korrosions- und Ätzwirkung sowie der schlechten Kontrollierbarkeit des Bleicheffekts keine Anwendung.It is generally customary to carry out the treatment for surface lightening of dyed textiles in an aqueous bath in a long liquor with hypochlorites, for example sodium hypochlorite. With chlorine bleach, an easily available, inexpensive and efficient bleaching agent is available, with a large number of dyes, u.a. Indigo or indigoid dyes, can be decolorized oxidatively. However, this approach has the disadvantage that large amounts of (adsorbable organically bound halogens) AOX-polluted wastewater incurred, which often have to be post-treated to comply with regulatory limits. Chlorine bleach is very toxic to aquatic organisms. Therefore, the use of chlorine-based chemicals in environmental and consumer organizations is highly criticized. In principle, the use of hypochlorites is also possible for local lightening, for example by spraying. In practice, however, this method is usually not used due to the strong corrosion and etching effects as well as the poor controllability of the bleaching effect.

Für die partielle Bleiche von Denim-Artikeln im Sprühverfahren ist die Verwendung von Kaliumpermanganat Stand der Technik. Allerdings sind auch hier in der Zwischenzeit gravierende Nachteile zu Tage getreten. So zeigt Kaliumpermanganat eine hohe Toxizität für Wasserorganismen und sein massiver Einsatz führt zu hohen Schwermetallgehalten im Abwasser. Gemäß Chemikalienverbotsverordnung (ChemVerV) erfordert die Abgabe von Kaliumpermanganat in Deutschland einen Verwendungsnachweis, um einer missbräuchlichen Verwendung zur Sprengstoff- oder Drogenherstellung vorzubeugen. Ähnliche Beschränkungen gibt es in zahlreichen, weiteren Ländern, was den Bezug von Kaliumpermanganat aufwändig macht und die Vorratshaltung erschwert. Darüber hinaus ist auch bei der Sprühbehandlung ein zusätzlicher Prozessschritt zur Entfernung des entstehenden Mangandioxids notwendig.For the partial bleaching of denim articles in the spray process, the use of potassium permanganate is state of the art. However, serious disadvantages have come to light here as well in the meantime. For example, potassium permanganate exhibits high toxicity to aquatic organisms and its massive use leads to high levels of heavy metals in wastewater. According to the Chemical Prohibition Ordinance (ChemVerV), the release of potassium permanganate in Germany requires a proof of use in order to avoid misuse for the production of explosives or drugs submissions. Similar restrictions exist in many other countries, making the purchase of potassium permanganate laborious and making stockholding more difficult. In addition, an additional process step to remove the resulting manganese dioxide is also necessary in the spray treatment.

Als Alternativen für Hypochlorit und Kaliumpermanganat wurde eine Reihe von Ansätzen vorgeschlagen, die aber ebenfalls gravierende Nachteile besitzen und sich in der Praxis nicht durchsetzen konnten.As alternatives for hypochlorite and potassium permanganate a number of approaches have been proposed, but also have serious disadvantages and could not prevail in practice.

So können u.a. Küpenfarbstoffe, speziell auch Indigo, durch Reduktionsmittel in die lösliche Leukoform umgewandelt, von der Faser entfernt und das Textil so aufgehellt werden. Bekannt ist zu diesem Zweck u.a. die Verwendung von Zuckern wie Glucose, so beschrieben in EP 0 654 557 A . Diese Verfahren besitzen jedoch den Nachteil, dass bei hohen Temperaturen (> 80 °C) und hoher Alkalinität (pH > 11) gearbeitet werden muss. Weiterhin fallen große Mengen an Abwasser an, die zudem durch die hohe organische Belastung einen erhöhten biologischen und chemischen Sauerstoffbedarf aufweisen. Diese Problematik tritt analog auch bei der Verwendung anderer Reduktionsmittel wie Ketoverbindungen, beispielsweise Hydroxyaceton, auf. Zudem sind reduzierende Verfahren zur Erzeugung lokaler Bleicheffekte grundsätzlich ungeeignet, da nicht wie in einer geschlossenen Waschtrommel eine insgesamt reduzierend wirkende Umgebung erzeugt werden kann und somit die lokal erzeugte Leukoform rasch durch Luftsauerstoff reoxidiert wird.For example, vat dyes, especially indigo, can be converted into the soluble leuco form by reducing agents, removed from the fiber, and the textile so lightened. Known for this purpose, inter alia, the use of sugars such as glucose, described in EP 0 654 557 A , However, these processes have the disadvantage that it is necessary to work at high temperatures (> 80 ° C.) and high alkalinity (pH> 11). Furthermore, large amounts of wastewater accumulate, which also have an increased biological and chemical oxygen demand due to the high organic load. This problem also occurs analogously when using other reducing agents such as keto compounds, for example hydroxyacetone. In addition, reducing processes for producing local bleaching effects are fundamentally unsuitable since, as in a closed washing drum, an overall reducing environment can not be produced and thus the locally produced leuco form is rapidly reoxidized by atmospheric oxygen.

Weiterhin ist die Verwendung von Ozon als Oxidationsmittel zur Aufhellung von gefärbten Baumwollstoffen bekannt ( EP 0 554 648 A ), wobei dieses Verfahren jedoch den Nachteil aufweist, dass es sich bei Ozon um ein sehr giftiges und ätzendes Gas handelt. Das führt dazu, dass die Handhabung von Ozon bei technischen Produktionsverfahren schwierig ist, da das gasförmige Ozon kontrolliert erzeugt, dem Behandlungsaggregat zugeführt und überschüssiges Ozon wieder abgeführt werden muss. Lokale Behandlungen beispielsweise von Denimartikeln sind auf diese Weise nicht möglich.Furthermore, the use of ozone as an oxidizing agent for lightening dyed cotton fabrics is known (US Pat. EP 0 554 648 A However, this method has the disadvantage that it is a very toxic and corrosive gas ozone. The result is that the handling of ozone in industrial production processes is difficult, since the gaseous ozone produced produced controlled to the treatment unit and excess ozone must be removed again. Local treatments such as denim articles are not possible in this way.

Auch die Verwendung von Wasserstoffperoxid oder Peressigsäure bei der Aufhellung von gefärbten Textilien ist bekannt. Diese Substanzen dienen aber nicht als primäres Bleichagens, sondern beispielsweise zur Neutralisierung eines bereits durch Kaliumpermanganat aufgehellten Baumwollstoffes bzw. zur Entfernung von dabei gebildeten MnO2-Anschmutzungen(vergleiche WO 92/13987 A ).The use of hydrogen peroxide or peracetic acid in the lightening of dyed textiles is also known. However, these substances do not serve as a primary bleaching agent, but for example to neutralize a cotton cloth brightened by potassium permanganate or for the removal of MnO 2 soils (cf. WO 92/13987 A ).

US 3,384,596 C offenbart die Verwendung von Peroxocarbonsäuren wie Monoperoxophthalsäure und m-Chlor-Peroxobenzoesäure in Gegenwart von Erdalkalisalzen als Bleichmittel bei alkalischem pH-Wert. US 3,384,596C discloses the use of peroxycarboxylic acids such as monoperoxophthalic acid and m-chloro-peroxobenzoic acid in the presence of alkaline earth salts as a bleaching agent at alkaline pH.

In US 4,443,352 C wird die Verwendung von Monoperoxophthalsäure und ihrer wasserlöslichen Salze als bleichverstärkender Bestandteil einer pulverförmigen Waschmittelformulierung vorgeschlagen. Als Verfahren genannt ist die Fleckbleiche in der Haushaltswäsche bei alkalischem pH-Wert. Eine analoge Verwendung von Monoperoxophthalsäure-Magnesiumsalz wird in EP 0 027 693 A beansprucht.In US 4,443,352 C there is proposed the use of monoperoxophthalic acid and its water-soluble salts as a bleach-enhancing component of a powdered detergent formulation. As a method called the stain bleach in the household laundry at alkaline pH. An analogous use of monoperoxophthalic acid magnesium salt is described in EP 0 027 693 A claimed.

DE 34 00 950 A offenbart die Verwendung von Monoperoxophthalsäure-Magnesiumsalz in Kombination mit einem Alkalibromid und Sulfonamiden in einer Waschmittelformulierung ebenfalls zur Fleckbleiche in der Haushaltswäsche bei alkalischem pH-Wert. DE 34 00 950 A discloses the use of monoperoxophthalic acid magnesium salt in combination with an alkali bromide and sulfonamides in a detergent formulation also for spot bleaching in household laundry at alkaline pH.

Vorgeschlagen wird in WO 95/25195 A die Verwendung einer Wasserstoffperoxidquelle in Kombination mit einem Eisensalz bei stark saurem pH zur Bleiche von Indigo-gefärbten Textilien. Diese Kombination ist als Fenton's Reagenz schon lange bekannt. Der Prozess ist aber sehr aufwändig und in der Praxis nicht wirtschaftlich darstellbar, denn das Eisensalz muss in einem vorgelagerten Behandlungsschritt aufgebracht und in einem nachgeschalteten Behandlungsschritt unter Verwendung großer Mengen an Komplexbildnern wieder entfernt werden. Zur Erzielung guter Effekte ist außerdem eine längere Behandlungszeit bei Temperaturen von 70 °C und höher notwendig, was diesen Prozess sehr energieintensiv macht.Proposed in WO 95/25195 A the use of a hydrogen peroxide source in combination with an iron salt at a strongly acidic pH for bleaching indigo-dyed textiles. This combination has long been known as Fenton's reagent. The process is very complex and not economically feasible in practice, because the iron salt must be applied in an upstream treatment step and removed in a subsequent treatment step using large amounts of complexing agents again. To achieve good effects, a longer treatment time at temperatures of 70 ° C and higher is also necessary, which makes this process very energy-intensive.

Dies trifft auch auf einen weiteren Vorschlag zur Aufhellung gefärbter Textilien zu: In WO 95/20643 A wird die Verwendung von Peroxodisulfaten als Sauerstoffquelle in Kombination mit einem Übergangsmetallkatalysator vorgeschlagen. Peroxodisulfate unterliegen aber als Oxidationsmittel den gleichen Beschränkungen nach der ChemVerV wie Permanganate und daher unter diesem Aspekt nicht als Alternative geeignet. Darüber hinaus sind Peroxodisulfat-Lösungen ebenso wie Fenton-Lösungen nicht zur Erzielung lokaler Effekte durch Sprüh- oder Pinselapplikation geeignet.This also applies to another proposal for the lightening of dyed textiles: WO 95/20643 A it is proposed to use peroxodisulfates as an oxygen source in combination with a transition metal catalyst. However, peroxodisulfates are subject to the oxidizing agent same restrictions according to the ChemVerV as permanganate and therefore under this aspect not suitable as an alternative. In addition, peroxodisulfate solutions as well as Fenton solutions are not suitable for achieving local effects by spray or brush application.

EP 0 176 124 A2 ( AT 44 763 E ) betrifft die Verwendung einer Suspension in Wasser, die als Bleichkomponente eine Peroxocarbonsäure enthält, welche von einer Dicarbonsäure mit 8 bis 13 Kohlenstoffatomen abgeleitet ist, als giessbares Bleichmittel. EP 0 176 124 A2 ( AT 44 763 E ) relates to the use of a suspension in water containing as bleach component a peroxycarboxylic acid derived from a dicarboxylic acid having 8 to 13 carbon atoms as a castable bleach.

DT 26 20 723 A1 betrifft Bleich- oder Reinigungsmittel, insbesondere mit einer Bleichwirkung bei niedrigen Temperaturen.DT 26 20 723 A1 relates to bleaching or cleaning agents, in particular with a bleaching effect at low temperatures.

DT 26 12 587 A1 betrifft Bleichmittelpräparate, die eine wasserlösliche aliphatische Peroxyverbindung sowie ein Verdickungsmittel aufweisen.DT 26 12 587 A1 relates to bleach preparations which comprise a water-soluble aliphatic peroxy compound and a thickener.

EP 0 160 342 A2 offenbart flüssige Bleichlösungen, die aliphatische Peroxyverbindungen als feste, partikuläre im Wesentlichen wasserunlösliche Bestandteile aufweisen. EP 0 160 342 A2 discloses liquid bleaching solutions comprising aliphatic peroxy compounds as solid, particulate, substantially water-insoluble constituents.

Weiterhin bekannt ist die Aufhellung von gefärbten Textilien in Gegenwart eines Enzyms. Beispiele sind die Verwendung von Laccase und einer Wasserstoffperoxidquelle als Oxidationsmittel ( US 5,851,233 C , WO 96/12846 A ). Diese Verfahren finden in der Praxis Anwendung, besitzen aber eine Reihe von Nachteilen. So wird auf Denim-Artikeln nur der Indigoanteil gebleicht, nicht aber das oftmals mitverwendete Schwefelschwarz. Zur Erzielung einer starken Aufhellung sind mehrere Behandlungsbäder notwendig, was diesen Prozess ebenfalls sehr kostenintensiv macht. Weiterhin muss auch diese Behandlung in langer Flotte erfolgen, ein partielles Aufhellen beispielsweise durch Sprühen ist nicht möglich.Also known is the lightening of dyed textiles in the presence of an enzyme. Examples are the use of laccase and a hydrogen peroxide source as the oxidizing agent ( US 5,851,233 C . WO 96/12846 A ). These methods are used in practice, but have a number of disadvantages. For example, only indigo content is bleached on denim articles, but not the often used sulfur black. To achieve a strong lightening several treatment baths are necessary, which also makes this process very expensive. Furthermore, this treatment must be carried out in a long liquor, a partial lightening, for example by spraying is not possible.

Es ist derzeit keine alternative Methode zur Verwendung von Kaliumpermanganat für die lokale Bleichbehandlung von Denimartikeln bekannt, die Anwendung in der Praxis findet.There is currently no alternative method of using potassium permanganate for the local bleaching treatment of denim articles which finds practical application.

Die Aufgabe der vorliegenden Erfindung ist es deshalb, ein Verfahren zum Aufhellen von gefärbten Textilien bereitzustellen, das es einerseits ermöglicht, das Textil flächig bzw. gleichmäßig in der gewünschten Nuance aufzuhellen, andererseits aber auch lokal begrenzt beispielsweise durch Sprüh- oder Pinselauftrag in frei wählbarer Intensität zu bleichen. Das Verfahren sollte in seiner aufhellenden Wirkung vergleichbare Ergebnisse wie unter Verwendung von chlorbasierten Bleichmitteln oder Kaliumpermanganat ermöglichen, dabei aber mögliche Nachteile und Gefahren für die Umwelt signifikant verringern. Insbesondere sollten keine umweltgefährlichen Chemikalien verwendet und ein Eintrag von AOX oder Schwermetallen ins Abwasser ausgeschlossen werden.The object of the present invention is therefore to provide a method for whitening dyed textiles, which on the one hand makes it possible to lighten the textile flatly or uniformly in the desired shade, but on the other hand also locally limited, for example, by spraying or brush application in freely selectable intensity to bleach. The process should provide comparable results in its lightening effect as using chlorine-based bleach or potassium permanganate, while significantly reducing potential environmental hazards and dangers. In particular, no environmentally hazardous chemicals should be used and an entry of AOX or heavy metals into the wastewater should be excluded.

Überraschenderweise wurde gefunden, dass organische Peroxocarbonsäuren, insbesondere bestimmte lineare oder cyclisch aliphatische oder aromatische Peroxocarbonsäuren oder -dicarbonsäuren, die hydrophobe Seitengruppen enthalten, bevorzugt Alkylreste mit wenigstens 5 C-Atomen, insbesondere bevorzugt mit 5 bis 30 C-Atomen und besonders bevorzugt mit Kettenlängen von 6 bis 10 C-Atomen, eine sehr hohe Aufhellungswirkung auf gefärbte Textilien besitzen. Insbesondere lassen sich Indigo und indigoide Farbstoffe unter moderaten Bedingungen bleichen, so dass eine lokale Behandlung, beispielsweise durch Sprühen, einfach und praxisgerecht durchgeführt werden kann.Surprisingly, it has been found that organic peroxycarboxylic acids, in particular certain linear or cyclic aliphatic or aromatic peroxocarboxylic acids or dicarboxylic acids containing hydrophobic side groups, preferably alkyl radicals having at least 5 carbon atoms, more preferably having 5 to 30 carbon atoms and more preferably having chain lengths of 6 to 10 C-atoms, have a very high whitening effect on dyed textiles. In particular, indigo and indigoid dyes can be bleached under moderate conditions, so that a local treatment, for example by spraying, can be carried out simply and practically.

Der Begriff "hydrophob" bezeichnet üblicherweise die Assoziation unpolarer Gruppen oder Moleküle einer wässrigen Umgebung. Damit werden Substanzen charakterisiert, die sich nicht mit Wasser mischen und es auf Oberflächen meist "abperlen" lassen.The term "hydrophobic" usually refers to the association of non-polar groups or molecules of an aqueous environment. This characterizes substances that do not mix with water and usually "roll off" on surfaces.

Unpolare Stoffe wie Fette, Wachse, Alkohole mit langen Alkylresten - also mit Ausnahme von Methanol, Ethanol und Propanol - Alkane, Alkene usw. sind hydrophob. Beim Lösen von hydrophoben Stoffen in Wasser tritt generell ein sogenannter hydrophober Effekt auf und bei manchen kleinen, hydrophoben Spezies, wie Methan oder Xenon, bilden sich sogar entropisch ungünstige Klathrat-Strukturen. Deshalb ist generell die Löslichkeit dieser Stoffe in Wasser gering.Non-polar substances such as fats, waxes, alcohols with long alkyl radicals - ie with the exception of methanol, ethanol and propanol - alkanes, alkenes etc. are hydrophobic. Dissolution of hydrophobic substances in water generally results in a so-called hydrophobic effect , and in some small, hydrophobic species, such as methane or xenon, even entropically unfavorable clathrate structures are formed. Therefore, the solubility of these substances in water is generally low.

Hydrophobe Stoffe sind so gut wie immer lipophil, das heißt, sie lösen sich gut in Fett und Öl auf. Oberflächen mit einem Kontaktwinkel von mehr als 90° gegenüber Wasser werden auch als hydrophob bezeichnet. Hydrophobe Reste im Sinne der vorliegenden Erfindung umfassen somit insbesondere einen zusammenhängenden Rest von wenigstens 5 C-Atomen, einer Kohlenstoffkette, die vorzugsweise mit Wasserstoffatomen abgesättigt sind um einen Alkylrest oder einen Arylrest bilden.Hydrophobic substances are almost always lipophilic, meaning they dissolve well in fat and oil. Surfaces with a contact angle of more than 90 ° to water are also referred to as hydrophobic. Hydrophobic radicals in the context of the present invention thus comprise, in particular, a contiguous radical of at least 5 C atoms, a carbon chain, which are preferably saturated with hydrogen atoms to form an alkyl radical or an aryl radical.

Erfindungsgemäße Bleichmittel sind aromatische Peroxocarbonsäuren, bestehend aus einem oder mehreren kondensierten aromatischen Ringen, gegebenenfalls substituiert mit einer oder mehreren weiteren Peroxocarbonsäuregruppen an beliebiger Position. Diese erfindungsgemäßen aromatischen Peroxocarbonsäuren können weiterhin substituiert sein mit mindestens einer funktionellen Gruppe, ausgewählt aus Alkyl-, Aryl-, Carboxylat-, Sulfonat-, Halogenid-, Nitro- oder Hydroxygruppen, an beliebiger Stelle am aromatischen Ringsystem. Als bevorzugte Beispiele sind zu nennen: Mono- oder Diperoxo-ortho, -meta oder -para-phthalsäure, Mono- oder Diperoxo-4-Methyl-o-phthalsäure, Mono- oder Diperoxo-1,8-Naphthalinsäure.Bleaching agents according to the invention are aromatic peroxycarboxylic acids consisting of one or more fused aromatic rings, optionally substituted with one or more further peroxycarboxylic acid groups at any position. These aromatic peroxycarboxylic acids of the invention may be further substituted with at least one functional group selected from alkyl, aryl, carboxylate, sulfonate, halide, nitro or hydroxy groups at any point on the aromatic ring system. Preferred examples are: mono- or diperoxo-ortho, -meta or -para-phthalic acid, mono- or diperoxo-4-methyl-o-phthalic acid, mono- or diperoxo-1,8-naphthalenic acid.

Die Peroxocarbonsäuren können sowohl in der Säureform als auch als Salze eingesetzt werden oder auch in situ durch die Zugabe von aktivierten Carbonsäurederivaten (beispielsweise als Anhydride) und einer Wasserstoffperoxidquelle oder in anderer Weise im Prozess erzeugt werden. Als Salze werden bevorzugt Alkali- oder Erdalkalisalze eingesetzt, beispielsweise Li-, Na-, K-, Mg- oder Ca-Salze.The peroxycarboxylic acids may be used both in the acid form and as salts or may also be generated in situ by the addition of activated carboxylic acid derivatives (for example as anhydrides) and a hydrogen peroxide source or otherwise in the process. The salts used are preferably alkali metal or alkaline earth metal salts, for example Li, Na, K, Mg or Ca salts.

Besonders überraschend wurde gefunden, dass die Behandlung unter sauren pH-Bedingungen besonders effizient durchgeführt werden kann, obwohl dem Fachmann bekannt ist, dass Peroxocarbonsäuren, beispielsweise Peressigsäure, bei einem pH-Wert in der Nähe des pKs-Werts, also im Neutralen bis schwach Alkalischen, die höchste Bleicheffizienz aufweisen. Im Rahmen der vorliegenden Erfindung werden textile Stoffe unter sauren pH-Bedingungen behandelt. Bevorzugt liegt der pH-Wert der Lösung im Bereich von pH1 bis pH5, besonders bevorzugt im Bereich von pH1,5 bis pH3,5.It has been found, particularly surprisingly, that the treatment under acidic pH conditions can be carried out particularly efficiently, although it is known to the person skilled in the art that peroxycarboxylic acids, for example peracetic acid, at a pH close to the pKa value, ie in the neutral to weakly alkaline , which have the highest bleaching efficiency. In the context of the present invention, textile fabrics are treated under acidic pH conditions. Preferably, the pH of the solution is in the range of pH1 to pH5, more preferably in the range of pH1.5 to pH3.5.

Als weitere Additive werden in die Anwendungsflotte native und synthetischer Verdickungsmittel, Salze wie Alkali- und Erdalkalisulfate, -phosphate sowie bei Bedarf Markierungsfarbstoffe, beispielsweise Farbstoffe, Netzmittel, Feuchthaltemittel wie Glycerin, Harnstoff, oder Dispergiermittel oder weitere Hilfsmittel zugesetzt. Der Einsatz von Farbstoffen (Markierungsstoffe dient der besseren visuellen Verfolgbarkeit des Sprühverlaufs. Dies ist besonders für die Praxis von Bedeutung, da das violette Permanganat die Sprühlösung stark färbt, während die erfindungsgemäße Sprühlösung grundsätzlich farblos ist.Native and synthetic thickening agents, salts such as alkali metal and alkaline earth metal sulfates, phosphates and, if required, marking dyes, for example dyes, wetting agents, humectants such as glycerol, urea or dispersants or more, are used as further additives in the application liquor Auxiliary added. The use of dyes (markers serves to better visual traceability of the spray course.) This is particularly important in practice, since the violet permanganate strongly colors the spray solution, while the spray solution according to the invention is basically colorless.

Die obengenannten pH-Bereiche stellen sich entweder bedingt durch die eingesetzten Reaktanden von selbst ein, können jedoch auch durch weitere Zusätze eingestellt werden. Besonders bevorzugt im Sinne der vorliegenden Erfindung wird der pH-Wert der Lösung mit Mineralsäuren oder organischen Säuren eingestellt. Ganz besonders bevorzugt in diesem Sinne sind wenig flüchtige Säuren, das heißt Säuren mit einem Dampfdruck < 20 Pa bei 20 °C, wie beispielsweise Citronensäure, Maleinsäure, Milchsäure, Phthalsäure, Phosphorsäure, Schwefelsäure oder Hydrogensulfate.The abovementioned pH ranges are established either automatically by the reactants used, but can also be adjusted by further additives. For the purposes of the present invention, the pH of the solution is particularly preferably adjusted with mineral acids or organic acids. Very particularly preferred in this sense are low-volatile acids, that is, acids having a vapor pressure <20 Pa at 20 ° C, such as citric acid, maleic acid, lactic acid, phthalic acid, phosphoric acid, sulfuric acid or hydrogen sulfates.

Dem Fachmann auf dem hier vorliegenden Gebiet stehen die verschiedensten Verfahren zum Inkontaktbringen der gefärbten Stoffe mit der Peroxocarbonsäure zur Verfügung. Besonders bevorzugt in diesem Sinne werden die gefärbten Stoffe mit einem Sprüh-, Tauch- oder Streichprozess vollständig oder teilweise mit der Peroxocarbonsäure oder ihre Salze enthaltenden Lösungen in Kontakt gebracht.A variety of methods for contacting the colored substances with the peroxycarboxylic acid are available to the person skilled in the art in this field. Particularly preferred in this sense, the colored substances are brought into contact with a solution containing all or part of the peroxycarboxylic acid or its salts by means of a spraying, dipping or brushing process.

Mit Hilfe der vorliegenden Erfindung können die verschiedensten Textilien beziehungsweise textilen Stoffe mit den Peroxocarbonsäuren in Kontakt gebracht werden. Besonders bevorzugt in diesem Sinne werden textile Stoffe aus Cellulosefasern oder aus Cellulosefasern in Mischung mit Natur- oder Synthesefasern eingesetzt, die mit den verschiedensten Farbstoffen gefärbt sind. Besonders bevorzugt im Sinne der vorliegenden Erfindung werden diese Farbstoffe ausgewählt aus den Gruppen der Küpen-, Direkt- oder Schwefelfarbstoffe.With the help of the present invention, a wide variety of textiles or textile fabrics can be brought into contact with the peroxycarboxylic acids. Particularly preferred in this sense are textile fabrics made of cellulose fibers or cellulose fibers in mixture with natural or synthetic fibers, which are dyed with a wide variety of dyes. Particularly preferred according to the present invention, these dyes are selected from the groups of vat, direct or sulfur dyes.

Das Verfahren der vorliegenden Erfindung eignet sich besonders für textile Stoffe, die mit Indigo, indigoiden Farbstoffen oder Schwefelschwarz sowie mit Kombinationen dieser Farbstoffe gefärbt sind.The process of the present invention is particularly suitable for textile fabrics dyed with indigo, indigoid dyes or sulfur black, as well as with combinations of these dyes.

Auch offenbart sind gebleichte Textilien, die nach einem Verfahren wie oben definiert erhältlich sind. Besonders bevorzugt im Sinne der Definition dieser gebleichten Textilien sind Jeans.Also disclosed are bleached fabrics obtainable by a method as defined above. Jeans, as defined by these bleached fabrics, are particularly preferred.

Die Wirkung der erfindungsgemäßen Flotten bei lokaler Bleichbehandlung wurde im direkten Vergleich zum Stand der Technik Kaliumpermanganat bestimmt. Sämtliche Peroxocarbonsäuren wurden in einer Konzentration eingesetzt, welche ungefähr der dreifachen Normalität einer heute durchschnittlich verwendeten 2% Kaliumpermanganat-Lösung entspricht.The effect of the liquors of the invention in local bleaching treatment was determined in direct comparison to the prior art potassium permanganate. All peroxycarboxylic acids were used at a concentration which is approximately three times the normality of a 2% potassium permanganate solution used on average today.

Der Bleicheffekt wurde auf zwei verschiedenen Denimwaren jeweils unter Bestimmung der Y-Werte nach CIE mit Datacolor International SF 600 Plus-CT, Blende 30 mm LAV, 4-fach-Messung, Kalibrierung Normlicht D 65 bestimmt.The bleaching effect was determined on two different denim products each with determination of the Y values according to CIE with Datacolor International SF 600 plus CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65.

Als Bleichergebnis sind erfindungsgemäß bevorzugt > 40% der Bleichwirkung einer Standard-KMnO4 Lösung erzielt worden, besonders bevorzugt >60% ganz besonders bevorzugt >80%.As bleaching result, according to the invention, preferably> 40% of the bleaching effect of a standard KMnO 4 solution has been achieved, particularly preferably> 60%, very particularly preferably> 80%.

Ausführungsbeispiele:EXAMPLES Referenzbeispiel 1:Reference Example 1:

Auf zwei handelsüblichen Denimwaren (Denim 1 = nicht entschlichtet, Scraping-Vorbehandlung mit Schleifpapier; Denim 2 = entschlichtet, Stonewash-Behandlung) wurde eine Rechteckfläche von 120 cm2 markiert und an den Kanten gegen die angrenzenden Flächen mit Klebefolie abgedeckt. Diese Flächen wurde mit je 2 g einer wässrigen Lösung von 20 g/l Kaliumpermanganat (0,38 normal) gleichmäßig besprüht und die Stoffmuster zur Kontrolle der Auftragsmenge anschließend gewogen. Nach einer Einwirkzeit von 20 min bei Raumtemperatur wurden die Stoffmuster in einer Waschschleudermaschine zusammen mit unbehandeltem Denim-Gewebe als Ballast zuerst 10 min bei 50 °C und einem Flottenverhältnis von 1:8 mit 4 g/l Natrium-Bisulfit neutralisiert, dann 3 mal kalt bei einem Flottenverhältnis von 1:10 gespült und anschließend im Tumbler getrocknet. Von den so erhaltenen Mustern wurde jeweils auf und neben der sprühbehandelten Fläche der Y-Wert nach CIE (Datacolor International SF 600 Plus-CT, Blende 30 mm LAV, 4-fach-Messung, Kalibrierung Normlicht D 65) gemessen und aus der Differenz der Grad der Aufhellung mit ΔY bestimmt.On two commercially available denim products (denim 1 = non-desized, scraping pretreatment with sandpaper, denim 2 = desized, stonewash treatment), a rectangular area of 120 cm 2 was marked and covered with adhesive film at the edges against the adjacent areas. These areas were uniformly sprayed with 2 g each of an aqueous solution of 20 g / l potassium permanganate (0.38 normal) and the fabric samples were then weighed to control the amount applied. After a reaction time of 20 min at room temperature, the fabric samples were neutralized in a washer-extractor together with untreated denim fabric as ballast first 10 min at 50 ° C and a liquor ratio of 1: 8 with 4 g / l sodium bisulfite, then 3 times cold rinsed at a liquor ratio of 1:10 and then dried in a tumbler. Of the patterns thus obtained, respectively on and In addition to the spray-treated area, the Y value measured according to CIE (Datacolor International SF 600 Plus CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65) and determined from the difference in the degree of lightening with ΔY.

Dabei ergaben sich Werte für Denim 1 von ΔY = 19,2 und für Denim 2 von ΔY = 35,0.The results were for denim 1 of ΔY = 19.2 and for denim 2 of ΔY = 35.0.

Vergleichsbeispiel 1:Comparative Example 1

Aus Monoperoxoglutarsäure (MPGS) wurde eine 1normale wässrige Lösung, enthaltend 15 Gew% MPGS, 2,5 Gew% Natriumsulfat und 0,4 Gew% Xanthan-Verdicker, hergestellt und mit Phosphorsäure auf einen pH-Wert von 2,9 eingestellt. Von dieser Lösung wurden 2,0 g auf beiden Standard-Denimwaren in gleicher Weise wie Referenzbeispiel 1 appliziert. Nach einer Einwirkzeit von 20 min bei 60 °C wurde das Stoffmuster in analoger Weise wie Referenzbeispiel 1 ohne Neutralisation 1 mal bei 40 °C und 1 mal kalt bei einem Flottenverhältnis von 1:10 gespült und anschließend im Tumbler getrocknet. Von den so erhaltenen Mustern wurde jeweils auf und neben der sprühbehandelten Fläche der Y-Wert nach CIE in analoger Weise wie Referenzbeispiel 1 gemessen und aus der Differenz der Grad der Aufhellung mit ΔY bestimmt.From monoperoxoglutaric acid (MPGS), a 1 normal aqueous solution containing 15% by weight of MPGS, 2.5% by weight of sodium sulfate and 0.4% by weight of xanthan thickener was prepared and adjusted to pH 2.9 with phosphoric acid. Of this solution, 2.0 g was applied to both standard denim goods in the same manner as Reference Example 1. After a contact time of 20 min at 60 ° C, the fabric sample was rinsed in a manner analogous to Reference Example 1 without neutralization 1 time at 40 ° C and 1 time cold at a liquor ratio of 1:10 and then dried in a tumbler. From the samples thus obtained, the Y value according to CIE was measured in each case on and next to the spray-treated surface in an analogous manner as Reference Example 1, and the degree of lightening with ΔY was determined from the difference.

Dabei ergaben sich Werte für Denim 1 von ΔY = 4,7 und für Denim 2 von ΔY = 8,3.The values for denim 1 were ΔY = 4.7 and for denim 2 ΔY = 8.3.

Vergleichsbeispiel 2:Comparative Example 2:

Analog zu Vergleichsbeispiel 1 wurde Monoperoxomaleinsäure (MPMS) als 1normale wässrige Lösung, enthaltend 13,8 Gew% MPMS, 2,5 Gew% Natriumsulfat und 0,4 Gew% Xanthan-Verdicker, mengengleich auf beiden Standard-Denimwaren appliziert, in gleicher Weise aufbereitet und vermessen.Analogously to Comparative Example 1, monoperoxomaleic acid (MPMS) was applied in the same way as a 1 normal aqueous solution containing 13.8% by weight of MPMS, 2.5% by weight of sodium sulfate and 0.4% by weight of xanthan thickener, the same amount being applied to both standard denim products and measure.

Dabei ergaben sich Werte für Denim 1 von ΔY = 4,9 und für Denim 2 von ΔY = 10,5.The values for denim 1 were ΔY = 4.9 and denim 2 were ΔY = 10.5.

Beispiel 1:Example 1:

Analog zu Vergleichsbeispiel 1 wurde handelsübliches Magnesium-bis-monoperoxophthalat-hexahydrat (MMPP) als 1normale wässrige Lösung, enthaltend 25 Gew% MMPP, 2,5 Gew% Natriumsulfat und 0,4 Gew% Xanthan-Verdicker, mengengleich auf beiden Standard-Denimwaren appliziert, in gleicher Weise aufbereitet und vermessen.Analogously to Comparative Example 1, commercially available magnesium bis-monoperoxophthalate hexahydrate (MMPP) was applied as a standard aqueous solution containing 25% by weight of MMPP, 2.5% by weight of sodium sulfate and 0.4% by weight of xanthan thickener on both standard denim goods , prepared and measured in the same way.

Dabei ergaben sich Werte für Denim 1 von ΔY = 18,7 und für Denim 2 von ΔY = 34,3.The results were for denim 1 of ΔY = 18.7 and for denim 2 of ΔY = 34.3.

Beispiel 2:Example 2:

Analog zu Vergleichsbeispiel 1 wurde Monoperoxophthalsäure (MPPS) als 1normale wässrige Lösung, enthaltend 16,8 Gew% MPPS, 2,5 Gew% Natriumsulfat und 0,4 Gew% Xanthan-Verdicker, mengengleich auf beiden Standard-Denimwaren appliziert, in gleicher Weise aufbereitet und vermessen.Analogously to Comparative Example 1, monoperoxophthalic acid (MPPS) was treated in the same way as 1 normal aqueous solution containing 16.8% by weight of MPPS, 2.5% by weight of sodium sulfate and 0.4% by weight of xanthan thickener, the same amount being applied to both standard denim products and measure.

Dabei ergaben sich Werte für Denim 1 von ΔY = 18,1 und für Denim 2 von ΔY = 32,2.The values for denim 1 were ΔY = 18.1 and denim 2 were ΔY = 32.2.

Vergleichsbeispiel 3:Comparative Example 3

Analog zu Vergleichsbeispiel 1 wurde Monoperoxo-cis-Cyclohexan-1,2-dicarbonsäure (MPDCS) als 1 normale wässrige Lösung, enthaltend 17,5 Gew% MPDCS, 2,5 Gew% Natriumsulfat und 0,4 Gew% Xanthan-Verdicker, mengengleich auf beiden Standard-Denimwaren appliziert, in gleicher Weise aufbereitet und vermessen.Analogously to Comparative Example 1, monoperoxo-cis-cyclohexane-1,2-dicarboxylic acid (MPDCS) as a normal aqueous solution containing 17.5% by weight of MPDCS, 2.5% by weight of sodium sulfate and 0.4% by weight of xanthan thickener, was the same volume applied on both standard denim products, processed and measured in the same way.

Dabei ergaben sich Werte für Denim 1 von ΔY = 12,4 und für Denim 2 von ΔY = 24,5.The values for denim 1 were ΔY = 12.4 and denim 2 were ΔY = 24.5.

Beispiel 4:Example 4:

Analog zu Vergleichsbeispiel 1 wurde Monoperoxo-4-Methyl-phthalsäure-Mg-Salz (MPMP) als 1 normale wässrige Lösung, enthaltend 18,4 Gew% MPMP, 2,5 Gew% Natriumsulfat, 0,4 Gew% Xanthan-Verdicker sowie zusätzlich 1 g/l eines Markierungsfarbstoffs mengengleich auf beiden Standard-Denimwaren appliziert. Der Markierungsfarbstoff wurde in den anschließenden Spülschritten wieder entfernt und diente nur dazu, den Sprühverlauf und die Gleichmäßigkeit des Auftrags besser sichtbar zu machen. Die Aufbereitung und Vermessung erfolgte in gleicher Weise wie in Vergleichsbeispiel 1.Analogously to Comparative Example 1, monoperoxo-4-methyl-phthalic acid Mg salt (MPMP) was added as a normal aqueous solution containing 18.4% by weight of MPMP, 2.5% by weight of sodium sulfate, 0.4% by weight of xanthan thickener and additionally 1 g / l of a marking dye is applied in the same amount on both standard denim products. The marking dye was removed in the subsequent rinsing steps and only served to make the spray history and the uniformity of the job more visible. The preparation and measurement were carried out in the same manner as in Comparative Example 1.

Dabei ergaben sich Werte für Denim 1 von ΔY = 18,9 und für Denim 2 von ΔY = 32,5.

Figure imgb0001
The values for denim 1 were ΔY = 18.9 and denim 2 were ΔY = 32.5.
Figure imgb0001

Beispiel 5:Example 5:

Aus handelsüblichem Magnesium-bis-monoperoxophthalat-hexahydrat (MMPP) wurden mehrere 1 normale wässrige Lösungen, enthaltend 25 Gew% MMPP, 2,5 Gew% Natriumsulfat und 0,4 Gew% Xanthan-Verdicker, hergestellt und mit Phosphorsäure auf pH-Werte zwischen 5,5 und 2,5 eingestellt. Von diesen Lösungen wurden 2,0 g auf der Standard-Denimware 2 in gleicher Weise wie Vergleichsbeispiel 1 appliziert, in gleicher Weise aufbereitet und vermessen.From commercially available magnesium bis-monoperoxophthalate hexahydrate (MMPP), several 1 normal aqueous solutions containing 25% by weight of MMPP, 2.5% by weight of sodium sulfate and 0.4% by weight of xanthan thickener were prepared and adjusted to pH values with phosphoric acid 5.5 and 2.5 set. Of these solutions, 2.0 g were applied to the standard denim 2 in the same manner as Comparative Example 1, processed in the same way and measured.

Die dabei erhaltenen Werte ΔY sind in Tabelle 2 zusammengefasst.

Figure imgb0002
The values ΔY obtained are summarized in Table 2 .
Figure imgb0002

Referenzbeispiel 2:Reference Example 2:

Standard Denimware 2 wurde auf einer Wasch-Schleudermaschine bei einem Flottenverhältnis von 1:8 mit einer Flotte, enthaltend 15 ml/l Na-Hypochloritlösung (120 g/l Aktivchlor), 15 min bei 50 °C behandelt. Anschließend wurde 2 x mit kaltem Weichwasser bei einem Flottenverhältnis von 1:10 gespült und im Anschluss daran in 2 Schritten zuerst mit 4 g/l Natriumbisulfit und dann mit 4 ml/l Wasserstoffperoxid 35% jeweils 10 min bei einem Flottenverhältnis von 1:10 und einer Temperatur von 40 °C neutralisiert. Nach Trocknung im Tumbler wurde bei einem Muster der Y-Wert nach CIE (Datacolor International SF 600 Plus-CT, Blende 30 mm LAV, 4-fach-Messung, Kalibrierung Normlicht D 65) bestimmt.
Dabei ergab sich ein Wert Y = 19,2Standard Denimware 2 was treated on a spin-on machine at a liquor ratio of 1: 8 with a liquor containing 15 ml / l Na hypochlorite solution (120 g / l active chlorine) for 15 min at 50 ° C. Subsequently, it was rinsed twice with cold soft water at a liquor ratio of 1:10 and then in 2 steps first with 4 g / l sodium bisulfite and then with 4 ml / l hydrogen peroxide 35% for 10 min at a liquor ratio of 1:10 and a temperature of 40 ° C neutralized. After drying in the tumbler, the Y-value was determined according to CIE (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65).
This resulted in a value Y = 19.2

Beispiel 6:Example 6:

Standard Denimware 2 wurde auf einer Wasch-Schleudermaschine bei einem Flottenverhältnis von 1:8 mit einer Flotte, enthaltend 20 g/l Magnesium-bis-monoperoxophthalat-hexahydrat (MMPP) und mit Citronensäure eingestellt auf einen pH-Wert von 3,0, 20 min bei 60 °C behandelt. Anschließend wurde 2 x mit Weichwasser bei 40 °C mit einem Flottenverhältnis von 1:10 gespült. Nach Trocknung im Tumbler wurde bei einem Muster der Y-Wert nach CIE (Datacolor International SF 600 Plus-CT, Blende 30 mm LAV, 4-fach-Messung, Kalibrierung Normlicht D 65) bestimmt.
Dabei ergab sich ein Wert Y = 17,8Standard Denimware 2 was applied to a washer-pulper at a liquor ratio of 1: 8 with a liquor containing 20 g / l of magnesium bis-monoperoxophthalate hexahydrate (MMPP) and adjusted with citric acid to a pH of 3.0, 20 min at 60 ° C treated. Subsequently, it was rinsed twice with soft water at 40 ° C. with a liquor ratio of 1:10. After drying in the tumbler, the Y-value was determined according to CIE (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65).
This resulted in a value Y = 17.8

Claims (9)

  1. A process for brightening dyed textile fabrics, characterized in that said fabrics are treated with an aqueous solution containing an aromatic organic peroxocarboxylic acid as an active component, under acidic pH conditions.
  2. The process according to claim 1, characterized in that an aromatic carboxylic acid with one or more percarboxy groups, optionally substituted with further functional groups, is employed as said peroxocarboxylic acid, for example, monoperoxo-orthophthalic acid, monoperoxo-metaphthalic acid, monoperoxo-paraphthalic acid, monoperoxo-4-methylphthalic acid, and/or monoperoxo-1,8-naphthalic acid.
  3. The process according to either of claims 1 to 2, characterized in that said brightening is performed at a pH within a range of from pH 1 to pH 5, especially at pH 1.5 to pH 3.5.
  4. The process according to any of claims 1 to 3, characterized in that said peroxocarboxylic acids are directly employed in the acid form or as salts, or obtained by the addition of activated carboxylic acid derivatives, such as anhydrides, and a hydrogen peroxide source.
  5. The process according to any of claims 1 to 4, characterized in that the pH of the solution is adjusted by mineral acids or organic acids, especially with low volatile acids having a vapor pressure of < 20 Pa at 20 °C, such as citric acid, maleic acid, lactic acid, phthalic acid, phosphoric acid, sulfuric acid, or hydrogensulfates.
  6. The process according to any of claims 1 to 5, characterized in that the dyed fabrics are contacted with a solution containing said peroxocarboxylic acid or salts thereof by a spraying, dipping or coating process.
  7. The process according to any of claims 1 to 6, characterized in that thickening agents, salts, marking dyes, wetting agents, humectants, dispersing agents and/or other auxiliary agents are added as further additives to the application liquors.
  8. The process according to any of claims 1 to 7, characterized in that textile fabrics made from cellulose fibers or cellulose fibers in admixture with natural or synthetic fibers, dyed with dyes selected from the groups of vat, direct or sulfur dyes are employed.
  9. The process according to claim 8, characterized in that textile fabrics dyed with indigo, indigoid dyes or sulfur black, and with combinations of such dyes are employed.
EP15717470.7A 2014-04-24 2015-04-15 Method for brightening dyed textiles Active EP3143193B1 (en)

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EP0027693B2 (en) 1979-10-18 1988-05-11 Interox Chemicals Limited Magnesium salts of peroxycarboxylic acids, processes for their preparation and their use as bleaching agents in washing compositions, and processes
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US20170051452A1 (en) 2017-02-23
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EP3143193A1 (en) 2017-03-22
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PT3143193T (en) 2019-05-29

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