EP1468139A2 - Procede de modification de la couleur de substrats textiles teints - Google Patents

Procede de modification de la couleur de substrats textiles teints

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Publication number
EP1468139A2
EP1468139A2 EP02791778A EP02791778A EP1468139A2 EP 1468139 A2 EP1468139 A2 EP 1468139A2 EP 02791778 A EP02791778 A EP 02791778A EP 02791778 A EP02791778 A EP 02791778A EP 1468139 A2 EP1468139 A2 EP 1468139A2
Authority
EP
European Patent Office
Prior art keywords
dyed
generated
inorganic
cell
reducing
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.)
Withdrawn
Application number
EP02791778A
Other languages
German (de)
English (en)
Inventor
Thomas Bechtold
Wolfgang Schrott
Peter Maier
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.)
Dystar Textilfarben GmbH and Co Deutschland KG
Original Assignee
Dystar Textilfarben GmbH and Co Deutschland KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dystar Textilfarben GmbH and Co Deutschland KG filed Critical Dystar Textilfarben GmbH and Co Deutschland KG
Publication of EP1468139A2 publication Critical patent/EP1468139A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/134—Fugitive dyeing or stripping 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
    • 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
    • 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
    • D06P5/153—Locally discharging the dyes with oxidants
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2016—Application of electric energy

Definitions

  • the present invention relates to a method for changing the color of dyed textile substrates by the action of reducing or oxidizing agents which are electrochemically produced in aqueous solution.
  • bleaching processes are of central importance, whereby their original task is to destroy the natural colored components of the fiber before the dyeing process.
  • Various methods are used for this.
  • Oxidized chlorine compounds hypochlorite, chlorine dioxide
  • Perborate compounds and percarbonates are widespread “bleaching chemicals” in the field of textile washing.
  • Reductive bleaching processes are used for azo dyes in various process stages.
  • the "etching" of a dye is usually based on the reductive destruction of azo dyes by the local application of reducing agents (formaldehyde sulfoxylates).
  • reducing agents formaldehyde sulfoxylates
  • false stains are "removed” again by using suitable reducing agents (sodium dithionite), i.e. decolorized so that the textile material can be dyed again.
  • sodium dithionite sodium dithionite
  • the complete destruction of the dye is in the foreground, so the conditions of use are chosen so that a deep bleaching is achieved.
  • iron-triethanolamine complexes can be used as regenerable reducing agents for dyeing vat dyes, sulfur dyes and indigo, and for decoloring azo dyes.
  • iron-triethanolamine complexes can be used as regenerable reducing agents for dyeing vat dyes, sulfur dyes and indigo, and for decoloring azo dyes.
  • other complexing agents such as gluconic acid,
  • DE 1 95 1 3 839 A1 describes a process for the electrochemical reduction of vat dyes using alkaline iron-triethanolamine complexes in an electrochemical arrangement with a high cathode area (graphite felt cathode). All these processes have in common that the electrochemical reduction is part of a dyeing process, ie the dye is completely reduced in each case. The latter also applies to the reductive destruction of the azo dye according to use example 3 of WO90 / 1 51 82.
  • the cathodically produced Fe (II) triethanolamine complex is used there to prepare a mis-dyed textile for subsequent re-dyeing.
  • hypochlorite The electrochemical on-site production of hypochlorite has already been extensively investigated, with the focus of the relevant publications on the production of hypochlorite-containing solutions for subsequent use in bleaching processes (Rengaranjan et.al., India. Bull. Electrochem. 1 993 9 (1 1 - 1 2) 642-643 and Tong C, CN881 01 765).
  • the anodic production of hypochlorite has also been described for textile washing and bleaching (see EP 0 002423 A1).
  • the decolorization of reactive dyes on textiles and in waste water by electrochemically generated hypochlorite was, for example, by Nishibe K.
  • the object of the present invention is therefore to provide a method which makes it possible to achieve defined and reproducible color changes on dyed or colored textiles. It has now been found that in order to achieve this object it is particularly important to adapt the electrochemical procedure to the textile material to be treated. This means that the setting of a suitable redox potential is extremely important.
  • the present invention relates to a method for achieving color changes on dyed textile substrates by treating the dyed textile substrates with an electrochemically produced aqueous solution of reducing or oxidizing agents, characterized in that the cell current is regulated so that the solution on the dyed textile substrate has suitable redox potential to achieve the color change.
  • color changes are understood to mean, in particular, brightening, color shifts and specific irregularities (microscopic or macroscopic).
  • the reducing agents or oxidizing agents required to achieve the desired color changes are usually produced electrochemically in an electrolysis cell or in a device which can take over the functions of an electrolysis cell according to the inventive method. This means that a suitable redox system or redox pair is introduced into the cell and the reducing or oxidizing agent is generated electrochemically therefrom.
  • Suitable electrolysis cells are known to the person skilled in the art. They usually consist of a working electrode, Gegenelektro.de, as well as power supply and power supply.
  • the cell may contain a membrane that separates the anode and cathode compartments, but depending on the redox system used, a simpler and less expensive undivided embodiment of the cell can also be used.
  • Particularly suitable electrolysis cells have a high active electrode area; accordingly, in addition to flat electrodes, for example in the form of plates, three-dimensional electrodes (screen plates, wire mesh, fleeces, felts, fleece electrodes, shake electrodes, porous sintered plates) are preferred, and multi-cathode systems are particularly preferred. When using large electrode areas, the required concentrations of active redox system can be kept low, which is particularly important for the economy of the method according to the invention.
  • Suitable electrode materials are known to the person skilled in the art and are to be selected according to requirements, with noble metals, stainless steel, graphite and carbon as well as noble metal oxide-coated titanium sheet being particularly preferred.
  • the electrolysis cell is advantageously designed as a flow cell which is connected directly to a treatment unit into which the aqueous solution (treatment solution) containing the reducing or oxidizing agents is pumped and in which the color change on the textile material is produced.
  • the solution can then be returned to the electrolysis cell and regenerated. There is no need to continuously load and unload the machine for preparatory rinse cycles or post-wash after the electrochemical treatment step.
  • a successive use of the electrolysis cell on a plurality of treatment units is advantageously carried out by coupling during the electrochemical treatment step and disconnecting the circulation after the treatment has ended.
  • the devices which are customary for wet finishing or washing of textiles can be used as treatment units. In particular, are for this Textile machines, such as yarn dyeing machine, jigger, jet dyeing machine or
  • the electrolysis cell is designed directly as a treatment unit, or parts of the treatment unit act as electrodes, so that electrolyte circulation between the electrolysis cell and treatment unit is eliminated.
  • the electrodes can be arranged in the immediate vicinity of the textile material, so that localized dye changes can be achieved.
  • the geometry of the electrodes depends on the desired result. If the electrode producing the reducing or oxidizing agent is pressed, for example in the form of a stamp, onto the textile containing electrolyte or in the treatment bath, a pattern-like color change can be generated after the current is switched on.
  • ready-made parts are e.g. Pants, drawn on electrically conductive supports of corresponding shape, which act as electrodes, and subjected to the method according to the invention.
  • the dyed textile material is subjected to mechanical and / or hydrodynamic stress simultaneously with the action of the reducing or oxidizing agent.
  • the mechanical stress arises, for example, from the movement of the goods in the rotating drum, and when treating colored textile goods in the form of strands or wide shapes, mechanical action can occur, for example, through squeezing mechanisms, rollers or rollers, for example, under-fleet crushing mechanisms, etc. respectively.
  • the mechanical stress that may be required can also be obtained by adding abrasive materials to the treatment solution. Suitable abrasive materials are, for example, pumice stone, suitable plastics or metals. Mechanical stress at the microscopic level can be achieved by adding suitable abrasive powders such as abrasives or metal powders.
  • a mechanical stress can also be coupled to a hydrodynamic stress, for example in a squeeze mechanism, in a
  • Drum washing machine during treatment in a jet dyeing machine or
  • a targeted hydrodynamic load can also be caused by an intensive liquor flow (spray pipes, suction,
  • Sieve drum washing machine or caused, for example, by vibration or ultrasound.
  • a suitable redox potential in the solution in the immediate vicinity of the colored textile substrate is the setting of a suitable redox potential in the solution in the immediate vicinity of the colored textile substrate.
  • the redox potential does not necessarily have to be kept constant at one value, but defined different redox potential levels can also follow one another.
  • the person skilled in the art can easily find out the redox potential required for the desired color change by simple experiments.
  • the redox potential of the treatment solution can be measured with a redox electrode, for example a Pt combination electrode with Ag / AgCI 3 M KCI reference electrode.
  • the measurement and control of the redox potential in the treatment solution can preferably be carried out by a so-called resting potential measurement, the working electrode simultaneously serving as a measuring electrode and the electrolysis current being interrupted during the time of the potential measurement.
  • the reference electrode can be attached next to the working electrodes, since the potential measurement is only carried out during the currentless period of the working electrode.
  • the measurement time required for a potential measurement is to be determined by preliminary tests, since a minimum period of time is required after the power has been switched off in order to allow the working electrode to adapt to the solution potential.
  • the redox potential is preferably measured in the treatment apparatus, particularly preferably in the immediate vicinity of the dyed textile substrate.
  • the necessary redox potentials depend on Dye and general conditions for oxidations preferably at + 1 00 to + 2000 mV, particularly preferably at + 400 to + 1 600 mV and in the case of reductions preferably at - 300 to -1 800 mV, particularly preferably at -400 to -1 200 mV.
  • the necessary potentials are set by regulating the cell current, current densities generally at 0.1 mA / cm 2 to 1 A / cm 2 , preferably at
  • the process according to the invention can be carried out with reducing or oxidizing agents.
  • Reducing agents are generated cathodically from reversible redox systems
  • oxidizing agents are generated anodically from reversible redox systems.
  • halides e.g. Sodium chloride or bromide
  • hypohalites formed by anodic oxidation, which are oxidizing agents.
  • all inorganic or organic redox systems can be used, with the help of which the necessary potential can be maintained. The person skilled in the art can therefore easily find suitable redox systems.
  • the process according to the invention is preferably carried out using inorganic reducing or oxidizing agents.
  • Suitable reducing agents are, for example: Cathodically generated metal complexes with inorganic or organic ligands, in which the metal is present in a low, i.e. reduced valence level, preferably iron (II) or tin (II) complexes with inorganic or organic ligands, iron (II) complexes which contain a 2-hydroxyethyl group or a polyhydroxycarboxylic acid in the ligand being particularly preferred.
  • Examples are triethanolamine and iron (II) - complexes of polyhydroxycarboxylic acids such as, for example, gluconic acid and heptagluconic acid, - substituted anthraquinone compounds, such as 1, 2 dihydroxyanthraquinone or anthraquinone sulfonic acids, tin (II) compounds, such as hexahydroxystannite in alkaline solutions, - produced by cathodionic reduction, d by cathodionic reduction, that can be used in neutral and weakly acidic solutions.
  • polyhydroxycarboxylic acids such as, for example, gluconic acid and heptagluconic acid
  • substituted anthraquinone compounds such as 1, 2 dihydroxyanthraquinone or anthraquinone sulfonic acids
  • tin (II) compounds such as hexahydroxystannite in alkaline solutions, - produced by cathodionic reduction, d by cath
  • Suitable oxidizing agents are, for example: Halogen-oxygen compounds, with hypochlorite and hypobromite being preferred.
  • the electrochemical production of mixtures of hypobromite and hypochlorite from mixtures of NaCl (0.01 mol / l to 5 mol / l) and NaBr (0.001 mol / I to 1 mol / l) is particularly preferred, which leads to an unexpected intensification of the bleaching effect.
  • the molar ratio of chloride: bromide is preferably between 5 and
  • Metal complexes with inorganic or organic ligands in which the metal is present in a high, i.e. oxidized valence stage is present preferably metal complexes of iron (III) and Mn (III) with inorganic or organic ligands, iron (III) -2,2'dipyridyl, Fe (III) hexycyanoferrate and Mn (III) (trans-cyclohexane 1, 2 diamine-N, N, N ', N'-tetraacetate) are particularly preferred, cycloaliphatic, heterocyclic or aromatic compounds which contain a NO, NOH or HNR-OH group, where 2,2,6, 6-tetramethyl-piperidin-1-yl ⁇ xyl (TEMPO) and violuric acid are particularly preferred, - hydrogen peroxide generated cathodically by oxygen reduction, and other electrochemically producible inorganic or organic peroxo compounds.
  • the reducing and oxidizing agents mentioned can in each case also be used in mixtures with one another, the mixing ratios with one another being uncritical
  • the reducing or oxidizing agents are preferably used in the concentration range from 0.1 mmol / l to 5 mol / l, particularly preferably between 1 mmol / l and 0.1 mol / l.
  • the process according to the invention is usually carried out at temperatures which are matched to the dye, redox system and in particular the color change to be achieved. Is preferably carried out between 15 ° C and 150 ° C, particularly preferably between 20 ° C and 95 ° C and very particularly preferably between 40 ° C and 60 ° C.
  • the colored textile substrates to be treated there are no technical restrictions with regard to the colored textile substrates to be treated, since the method according to the invention can be adapted to the material. They can be in the form of fibers, yarns, fabrics, knitwear or as fully or partially assembled products.
  • the dyed textile substrates preferably consist of fiber materials
  • Cellulose fibers are, synthetic fibers or mixtures of the fibers mentioned.
  • Dyed textile substrates made of cellulose fibers and their are particularly preferred
  • dyes there are also no restrictions on the dyes to be changed.
  • reactive dyes vat dyes, sulfur dyes, noun dyes, naphthol dyes, disperse dyes, acid dyes, cationic dyes or metal complex dyes can be changed according to the invention.
  • All dye classes customary for this substrate can be used for cellulose fibers, with reactive dyes, vat dyes, sulfur dyes or noun dyes being preferred.
  • substrates made of polyester fibers can be colored with disperse dyes.
  • Indigo-dyed cotton substrates can be treated particularly preferably by the process according to the invention.
  • the dye and redox system must of course be coordinated, i.e. the reducing or oxidizing agent must react with the dye and thus be able to change the color.
  • dyes containing azo groups can be reductively cleaved or indigo can be subjected to reversible dye reduction.
  • the treatment solution should preferably be circulated between the treatment unit and the electrolysis cell in such a way that it is generated electrochemically
  • Amount of active chemicals can also be transported into the treatment unit and the predetermined concentration of chemicals to be converted does not limit the current density of the electrolysis cell. This adjustment can be carried out using conventional calculations based on the electrolysis current and the concentration of the redox system used. If, for example, with a cell current of 20 A and a concentration of redox system of 0.05 mol / l, the concentration of the starting chemical should not drop below 0.04 mol / l, a circulation rate of 1.24 l / min between the treatment unit and the cell is required.
  • Other parameters that may need to be taken into account in the process according to the invention are liquor ratio, pH value, and auxiliaries such as dispersants, detergents, lubricants or enzymes. The liquor ratio must be taken into account, since a certain concentration of active chemicals is generated by the redox potential and depending on
  • Figure 1 schematically shows an arrangement which is suitable for carrying out the method according to the invention.
  • an electrolysis cell consisting of working electrode b, membrane d, counterelectrode e, current leads c and
  • Power supply a produces the reducing agent or oxidizing agent (desired form of the redox pair used) in solution k, which is pumped through a circulation g into the treatment unit m.
  • the colored textile substrate f to be treated is located in the treatment unit and is subjected to additional mechanical and / or hydrodynamic stresses there.
  • the redox potential in the solution h in the treatment unit is detected by the redox measuring device i.
  • the supply current strength of the cell current supply a is adjusted via the Control loop I. This makes it possible to control the redox potential and thus the treatment effect to be achieved with the dyed textile substrate.
  • the treatment solution is discharged from the treatment unit via the outlet j, which then carries out, for example, rinsing processes with the textile substrate.
  • the drained treatment solution can be supplied for regeneration.
  • FIG. 2 shows an arrangement in which the electrolysis cell and treatment unit form a unit and the electrodes are arranged in the immediate vicinity of the colored textile substrate to be treated, as well as the two working phases.
  • the dyed textile substrate f to be treated contains the amount of electrolyte required for the electrolysis, therefore the cell content h and treatment solution k are identical. Since, for geometric reasons, a potential measurement is only possible with relatively great effort, the measurement is carried out after the power supply has been interrupted as a so-called quiescent potential measurement using the line i, which is connected to the working electrode b, and the reference electrode n. Potential measurement and current control are carried out to set the desired redox potential therefore intermittent.
  • Example 1 Brightening indigo with hypochlorite at pH 1 0.0-1 0.2 Structure of the electrolytic cell:
  • Anode titanium expanded metal with Pt mixed oxide coating, two electrodes, each active length 1 0 cm, width 3.0 - 3.1 cm.
  • Diaphragm Nafion cation exchange membrane
  • Cathode stainless steel approx. 1 00 cm 2
  • the circulation of the treatment apparatus - electrolysis cell is carried out by a peristaltic pump with a capacity of 1 50 ml / min.
  • the liquor is moved by a magnetic stirrer (500 rpm) with heating.
  • the Pt electrode and reference electrode, as well as the temperature and a pH measurement, are located in the vessel.
  • the pH constancy during electrolysis is adjusted by dosing alkali in the anolyte.
  • Anolyte volume 850 ml, 1 g / l soda pA and 10 g / l NaCI pA catholyte volume: 350 ml.
  • Catholyte composition as anolyte. Goods weight 1 1, 1 8 g indigo-dyed cotton fabric (denim).
  • a redox potential of + 440 to + 470 mV at a pH value of 1 0.0 to 1 0.2 is set over a period of 35 min by regulating the cell current in the range from 100 mA to 500 mA (cell voltage 2.40 to 5, 1 0 V).
  • sample 1 1 5 minutes and sample 2 are treated 35 minutes.
  • Anolyte volume 850 ml, 0.5 g / l soda p.A., 0.5 g / l Na bicarbonate and 10 g / l NaCl p.A., catholyte composition like anolyte.
  • a redox potential of + 700 to + 720 mV at a pH of 8.1 is measured over a period of 32 minutes, adjusted by regulating the cell current in the range from 200 mA to 500 mA (cell voltage 3.1 0 to 4.80 V) ).
  • Sample 1 is treated under these conditions for 1 2 minutes, sample 2 for 32 minutes.
  • Treated Pattern 2 27.48 + 0.99 -14.33
  • Anolyte volume 800 ml, 1.0 g / l soda p.A., 0.1 g / l Na bicarbonate and 10 g / l NaCI p.A. , Catholyte composition such as anolyte.
  • a redox potential of + 455 to + 555 mV at a pH value of 1 0.5 is measured over a period of 45 minutes, adjusted by regulating the cell current in the range from 0 mA to 500 mA (cell voltage 5.1 5 V).
  • Sample 1 is treated under these conditions for 25 minutes, sample 2 for 45 minutes.
  • Treated pattern 1 26.75 + 0.72 -14.31
  • Anolyte volume 800 ml, 0.5 g / l soda p.A., 0.5 g / l Na bicarbonate and 10 g / l NaCI p.A., 0.1 g / l potassium bromide, catholyte composition like anolyte.
  • a redox potential of + 720 to + 750 mV at a pH of 8.1 to 8.6 is measured over a period of 40 minutes, adjusted by regulating the
  • Sample 1 is treated under these conditions for 20 minutes, sample 2 for 40 minutes.
  • Treated sample 1 48.89 -5.78 -2.56
  • Treated sample 2 54.27 -6.05 + 0.89
  • Anolyte volume 800 ml, 0.5 g / l soda p.A., 0.5 g / l Na bicarbonate, 10 g / l NaCI p.A. and 0.1 g / l potassium bromide, catholyte composition such as anolyte.
  • Sample 1 is treated under these conditions for 10 minutes, sample 2 for 30 minutes.
  • the samples taken are rinsed in cold water, spun and dried at 110 ° C.
  • Anolyte volume 800 ml, 1.0 g / l Na bicarbonate, 10 g / l NaCI p.A. and 0.1 g / l
  • Potassium bromide catholyte composition such as anolyte.
  • Sample 1 is treated under these conditions for 33 minutes, sample 263 minutes.
  • Treated pattern 1 28.32 + 0.27 -15.18
  • Treated Pattern 2 28.41 + 0.11 -15.31
  • Anolyte volume 800 ml, 1.0 g / l Na bicarbonate, 10 g / l NaCI p.A. and 0.1 g / l
  • Potassium bromide catholyte composition such as anolyte.
  • a redox potential of +759 to +825 mV at a pH value of 7.7 to 8.3 is measured over a period of 30 minutes, adjusted by regulating the
  • Sample 1 is treated under these conditions for 10 minutes, sample 230 minutes. The samples taken are rinsed in cold water, spun and added
  • Treated pattern 1 35.17 -3.05 -11.55
  • Example of use 8 - lightening of reactive-colored " goods with violuric acid at pH 4.6 The structure of the electrolytic cell and the implementation of the method are carried out as
  • Anolyte volume 770 ml, 1.0 g / l violuric acid, 1 2 g / l acetic acid and 4 g / l NaOH,
  • Catholyte 300 ml sodium hydroxide solution 40g / l. Goods weight 4, 1 g reactive-dyed cotton (red).
  • a redox potential of + 604.7 to + 633 mV is measured at a pH of 4.6 over a period of 36 minutes, adjusted by regulating the cell current in the cell
  • Sample 1 is treated under these conditions for 1 6 minutes, sample 2 for 36 minutes.
  • Treated pattern 1 43.57 + 58.80 + 3.1 1
  • Treated pattern 2 44.54 + 57.51 + 2.91
  • Anolyte volume 800 ml, 1.0 g / l violuric acid, 1 2 g / l acetic acid and 4 g / l NaOH,
  • Catholyte 300 ml sodium hydroxide 40g / l. Goods weight 4.55 g reactive-dyed cotton (red).
  • a redox potential of + 608.7 to + 661 mV is measured at a pH of 4.6 over a period of 55 minutes, adjusted by regulating the cell current in the cell
  • Sample 1 is treated under these conditions for 31 minutes, sample 2 for 55 minutes.
  • Anolyte volume 800 ml, 1.0 g / l violuric acid, 1 2 g / l acetic acid and 4 g / l NaOH, catholyte: 300 ml sodium hydroxide solution 40g / l.
  • a redox potential of + 564 to + 61 5 mV at a pH value of 4.6 is measured over a period of 31 minutes, adjusted by regulating the cell current in the range from 200 mA to 500 mA (cell voltage 3.25 to 5.2 V) ,
  • Sample 1 is treated under these conditions for 1 minute, sample 2 for 31 minutes.
  • Treated pattern 1 1 9.72 + 0.10 -0.41
  • Anolyte volume 800 ml, 1.0 g / l violuric acid, 1 2 g / l acetic acid and 4 g / l NaOH, catholyte: 300 ml sodium hydroxide solution 40g / l.
  • Range from 0 mA to 500 mA (cell voltage 5.2V).
  • Sample 1 is treated under these conditions for 20 minutes, sample 2 for 40 minutes.
  • Treated pattern 2 1 8.94-0, 1 3 -0.22
  • Example of use 1 2 - Local dye destruction with hypochlorite / potassium bromide A nr ⁇ ⁇ indigo or red reactive dye-dyed tissue (for example with the mass 1 2.4 g) is mixed with four times the amount (approx. 50 ml) of a solution of 1.0 g / l Na bicarbonate, 10 g / l NaCl pA and 0.1 g / l potassium bromide.
  • a Pt electrode with an area of 2.25 cm 2 serves as the working electrode
  • a stainless steel electrode serves as the counter electrode.
  • the potential of the working electrode is measured against an Ag / AgCI 3M KCI after the current has been interrupted, the measurement being carried out after a waiting time of 2 minutes for setting the potential.
  • Example of use 13- Local dye destruction by iron (II / III) complexes A tissue dyed with indigo or red reactive dye (for example with a mass of 12.4 g) is mixed with four times the amount (approx. 50 ml) of 0.024 mol / l iron ( ll) wetted complex solution (triethanolamine and polyhydroxycarboxylic acid as lignades).
  • a Pt electrode with an area of 2.25 cm 2 serves as the working electrode, a stainless steel electrode serves as the counter electrode.
  • the potential of the working electrode is measured against an Ag / AgCI 3M KCI after the current has been interrupted, the measurement being carried out after a waiting time of 2 minutes for setting the potential.
  • the color changes achieved as a function of the redox potential achieved are shown in Table 2.
  • Starting pattern indigo see application example 1
  • starting pattern red reactive dye see application example 8.

Abstract

Procédé permettant d'obtenir des modifications de la couleur de substrats textiles teints par traitement desdits substrats avec une solution aqueuse, produite de manière électrochimique, de substances de réduction ou d'oxydation. Ledit procédé est caractérisé en ce que le courant cellulaire est ainsi réglé que la solution en contact avec le substrat textile teint possède un potentiel d'oxydo-réduction approprié pour obtenir une modification de la couleur.
EP02791778A 2001-12-13 2002-12-05 Procede de modification de la couleur de substrats textiles teints Withdrawn EP1468139A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10161265 2001-12-13
DE10161265A DE10161265A1 (de) 2001-12-13 2001-12-13 Verfahren zur Farbveränderung von gefärbten textilen Substraten
PCT/EP2002/013778 WO2003054289A2 (fr) 2001-12-13 2002-12-05 Procede de modification de la couleur de substrats textiles teints

Publications (1)

Publication Number Publication Date
EP1468139A2 true EP1468139A2 (fr) 2004-10-20

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US (1) US20050028291A1 (fr)
EP (1) EP1468139A2 (fr)
CN (1) CN1306110C (fr)
AU (1) AU2002358095A1 (fr)
BR (1) BR0214839A (fr)
CA (1) CA2470080A1 (fr)
DE (1) DE10161265A1 (fr)
HK (1) HK1073142A1 (fr)
MX (1) MXPA04005676A (fr)
TW (1) TWI276667B (fr)
WO (1) WO2003054289A2 (fr)

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US20050028291A1 (en) 2005-02-10
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CA2470080A1 (fr) 2003-07-03
TWI276667B (en) 2007-03-21
WO2003054289A2 (fr) 2003-07-03
AU2002358095A1 (en) 2003-07-09
CN1306110C (zh) 2007-03-21
CN1620536A (zh) 2005-05-25
HK1073142A1 (en) 2005-09-23
WO2003054289A3 (fr) 2004-08-05
MXPA04005676A (es) 2004-12-06
DE10161265A1 (de) 2003-06-26

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