EP0654557B1 - Procédé de blanchiment d'articles denim teints à l'indigo - Google Patents

Procédé de blanchiment d'articles denim teints à l'indigo Download PDF

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Publication number
EP0654557B1
EP0654557B1 EP94890191A EP94890191A EP0654557B1 EP 0654557 B1 EP0654557 B1 EP 0654557B1 EP 94890191 A EP94890191 A EP 94890191A EP 94890191 A EP94890191 A EP 94890191A EP 0654557 B1 EP0654557 B1 EP 0654557B1
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EP
European Patent Office
Prior art keywords
bleaching
accordance
indigo
vat
articles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94890191A
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German (de)
English (en)
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EP0654557A1 (fr
Inventor
Vinzenz Dipl.-Ing. Olip
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP0654557A1 publication Critical patent/EP0654557A1/fr
Application granted granted Critical
Publication of EP0654557B1 publication Critical patent/EP0654557B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/155—Locally discharging the dyes with reductants
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—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 denim articles or warp bodies consisting entirely or partially of cellulosic materials with a chain dyed with indigo vat dyes and predominantly 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., Irishr fraverlag 1989, pages 80-81).
  • 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. 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 Cl 2 in the wastewater from these plants 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 best known reducing agents used in vat dyeing of cellulose fibers are sodium dithionite, formamidine sulfinic acid (thiourea dioxide) and hydroxyacetone.
  • DE-A-38 31 098 describes an active ingredient combination for a means for decolorizing, peeling off false colors and lightening colored textiles.
  • the combination consists of thiourea dioxide (formamidine sulfinic acid) and carbonates, for example soda, or phosphates, for example trisodium phosphate.
  • DE-A-21 65 154 describes a process for the alkaline pretreatment and bleaching of textile material containing cotton under high-temperature steaming conditions in a short liquor.
  • a reducing agent including formamidine sulfinic acid, is added in order not to have to accept a loss in the average polymerization value despite the use of the alkaline pretreatment and to avoid damage to the cellulose from atmospheric oxygen.
  • JP-A-57 191 382 describes the mercerization of textiles dyed with vat dyes in the presence of reducing agents, including formamidine sulfinic acid, with this treatment the original color is restored and the color depth is leveled out.
  • the object of the invention is therefore to avoid the disadvantages mentioned above, to produce uniformly lightened denim articles without dyeing the predominantly white weft thread and Change color depth. Chlorine and organochlorine compounds in waste water should be prevented.
  • the process according to the invention consists in exposing the above-mentioned fabric to an alkaline aqueous bath at elevated temperatures, in which a combination of formamidine sulfinic acid and carbohydrates with the general gross formula C n H 2n O n in a weight ratio of 80:20 to 99: 1 is used as the bleaching agent .
  • a combination of formamidine sulfinic acid and carbohydrates with the general gross formula C n H 2n O n in a weight ratio of 80:20 to 99: 1 is used as the bleaching agent .
  • 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 alkaline aqueous medium, in particular at pH values of 10-13, preferably at about 12.5, using the reducing agent mixtures mentioned, ie mixtures of formamidine sulfinic acid (thiourea dioxide) with carbohydrates with the general gross formula C n H 2n O n and at temperatures of preferably above 50 ° C.
  • 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 is 80:20 to 99: 1.
  • the pH is preferably adjusted by adding NaOH.
  • Other bases such as KOH can be used.
  • the denim articles are placed in fresh water after being stoned and the temperature is raised to above 50 ° 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.
  • the bleaching time can be 1 to 30 minutes, preferably 15 minutes.
  • the reducing agent mixtures are used in amounts of preferably 0.5 to 10%, in particular 2 or 4%, depending on the desired brightness.
  • the liquor is preferably drained off after this treatment and the denim articles are preferably rinsed with water at 40 ° C.
  • the second rinsing bath is preferably 2 g / l acetic acid conc. and 1 g / l of hydrogen peroxide were added.
  • the denim articles are then preferably spun and dried.
  • 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 O 2 / l and is free from 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 wastewater after a bleaching with sodium hypochlorite showed a COD value of 18600 mg O 2 / l.

Claims (7)

  1. Procédé pour le blanchiment d'articles denim ou de corps de chaîne avec des chaînes colorées à l'aide de colorants de cuve indigoïdes et de trame essentiellement blanche, constitués partiellement ou totalement en matériaux cellulosiques, par traitement dans un milieu alcalin aqueux à température élevée sans coloration des fils de chaîne essentiellement blancs, caractérisé en ce que l'on utilise comme agent de blanchiment une combinaison d'acide formamidine-sulfinique et d'hydrates de carbone présentant la formule générale brute CnH2nOn dans un rapport pondéral de 80:20 à 99:1.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre comme hydrate de carbone présentant la formule brute générale CnH2nOn, des monosaccharidesà effet réducteur.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise comme monosaccharide à effet réducteur, le glucose.
  4. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme hydrate de carbone, des oligosaccharides.
  5. Procédé selon la revendication 4, caractérisé en ce qu'on utilise comme oligosaccharide, du saccharose.
  6. Procédé selon la revendication 1, caractérisé en ce que le blanchiment s'effectue à des rapports de bain de 1:1 à 1: 40.
  7. Procédé selon la revendication 6, caractérisé en ce que le blanchiment s'effectue à des rapports de bain de 1:5 à 1:7.
EP94890191A 1993-11-23 1994-11-22 Procédé de blanchiment d'articles denim teints à l'indigo Expired - Lifetime EP0654557B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT2378/93 1993-11-23
AT0237893A AT401274B (de) 1993-11-23 1993-11-23 Verfahren zum bleichen von textilartikeln

Publications (2)

Publication Number Publication Date
EP0654557A1 EP0654557A1 (fr) 1995-05-24
EP0654557B1 true EP0654557B1 (fr) 1997-03-12

Family

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Family Applications (1)

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EP94890191A Expired - Lifetime EP0654557B1 (fr) 1993-11-23 1994-11-22 Procédé de blanchiment d'articles denim teints à l'indigo

Country Status (3)

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EP (1) EP0654557B1 (fr)
AT (2) AT401274B (fr)
DE (1) DE59402052D1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19606620C2 (de) * 1996-02-22 1999-01-07 Henkel Kgaa Verfahren zur reduktiven Bleiche
DE19708973A1 (de) * 1997-03-05 1998-09-10 Basf Ag Verfahren zum Aufhellen von gefärbtem Gewebe
CZ299860B6 (cs) * 2003-09-02 2008-12-17 Zpusob odstranení chloru v lázni na praní
DE102014207727A1 (de) 2014-04-24 2015-10-29 Cht R. Beitlich Gmbh Verfahren zum Aufhellen von gefärbten Textilien
SE541675C2 (en) 2016-10-19 2019-11-26 Re Newcell Ab Recycling of cellulosic textiles
MX2020002536A (es) * 2017-10-25 2020-10-01 CHT Germany GmbH Procedimiento de eliminacion de depositos de oxido de manganeso de superficies textiles.
EP4053328A1 (fr) 2021-03-02 2022-09-07 CHT Germany GmbH Traitement combiné de blanchiment pour textiles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3831098A1 (de) * 1988-09-13 1990-03-22 Ludwig Plack Wirkstoffkombination fuer ein mittel zum entfaerben, abziehen von fehlfaerbungen und aufhellen von gefaerbten textilien

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Publication number Priority date Publication date Assignee Title
BE792583A (fr) * 1971-12-28 1973-06-12 Peroxid Chemie Gmbh Procede de pre-traitement et de blanchiment des matieres textiles
SU676662A1 (ru) * 1976-04-05 1979-07-30 Уральский филиал Всесоюзного научно-исследовательского и проектного института химической промышленности Отбеливающий состав "диола"
DE3113732A1 (de) * 1981-04-04 1982-10-21 Basf Ag, 6700 Ludwigshafen Verfahren zum bedrucken von synthesefasern
JPS57191382A (en) * 1981-05-14 1982-11-25 Mitsui Toatsu Chemicals Treatment of dyed article by indanethrone vat dye
DE3433926A1 (de) * 1984-09-15 1986-03-27 Basf Ag, 6700 Ludwigshafen Verfahren zum einbadigen reduktiven und oxidativen bleichen von wolle
JPS61195199A (ja) * 1985-02-25 1986-08-29 旭電化工業株式会社 還元剤組成物
JPH0196297A (ja) * 1987-10-09 1989-04-14 Lion Corp 漂白剤組成物
DE3833194A1 (de) * 1988-09-30 1990-04-05 Basf Ag Verfahren zum faerben von textilen materialien aus cellulosefasern
US5366510A (en) * 1992-06-09 1994-11-22 Eric Wasinger Process for desizing and color fading garments
EP0583745A1 (fr) * 1992-08-18 1994-02-23 Hoechst Aktiengesellschaft Procédé de teinture de fibres cellulosiques avec des colorants au soufre
JP3225473B2 (ja) * 1993-03-12 2001-11-05 旭電化工業株式会社 安定性及び流動性の向上した二酸化チオ尿素の製造法

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Publication number Priority date Publication date Assignee Title
DE3831098A1 (de) * 1988-09-13 1990-03-22 Ludwig Plack Wirkstoffkombination fuer ein mittel zum entfaerben, abziehen von fehlfaerbungen und aufhellen von gefaerbten textilien

Also Published As

Publication number Publication date
ATE150106T1 (de) 1997-03-15
DE59402052D1 (de) 1997-04-17
ATA237893A (de) 1995-12-15
AT401274B (de) 1996-07-25
EP0654557A1 (fr) 1995-05-24

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