WO2009051569A2 - Procédé de teinture de matériaux textiles à base de cellulose et de polyamide faisant appel à de l'indigo réduit par des enzymes - Google Patents

Procédé de teinture de matériaux textiles à base de cellulose et de polyamide faisant appel à de l'indigo réduit par des enzymes Download PDF

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WO2009051569A2
WO2009051569A2 PCT/SI2008/000054 SI2008000054W WO2009051569A2 WO 2009051569 A2 WO2009051569 A2 WO 2009051569A2 SI 2008000054 W SI2008000054 W SI 2008000054W WO 2009051569 A2 WO2009051569 A2 WO 2009051569A2
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Prior art keywords
indigo
dyeing
dyed
dye
polyamide
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PCT/SI2008/000054
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English (en)
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WO2009051569A3 (fr
Inventor
Mojca Bozic
Georg GÜBITZ
Vanja Kokol
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Univerza V Mariboru Fakulteta Za Strojnistvo
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Priority claimed from SI200700264A external-priority patent/SI22629A/sl
Priority claimed from SI200800219A external-priority patent/SI22867A/sl
Application filed by Univerza V Mariboru Fakulteta Za Strojnistvo filed Critical Univerza V Mariboru Fakulteta Za Strojnistvo
Publication of WO2009051569A2 publication Critical patent/WO2009051569A2/fr
Publication of WO2009051569A3 publication Critical patent/WO2009051569A3/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/221—Reducing systems; Reducing catalysts
    • 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
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/243—Polyamides; Polyurethanes using vat or sulfur dyes, indigo
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes

Definitions

  • This invention relates to the dyeing process of cellulose and polyamide-based textile materials by indigo dye (C.I. Vat Blue 1) using enzymes for indigo reduction.
  • indigo dye C.I. Vat Blue 1
  • the technical problem lies in the high cost and negative environmental impact of the current process of dyeing cellulose and polyamide fibers with vat, respectively indigoid dyes.
  • the waste water may contain considerable excess of the reducing agent, so an addition of oxidation agent is required for water stabilization.
  • This additionally increases toxicity; effects on the aerobic processes and consequently increase the cost of treatment.
  • Disposal of the dyeing bath also contains excess of alkalies, salts, surfactants and remain dye.
  • reduction agent sodium dithionite
  • Conventional reduction procedure of indigo in high alkaline medium with sodium dithionite is a technological known process for dyeing cellulose fibers and it is not suitable for dyeing of polyamide fibers.
  • Polyamide is negatively charged in alkaline medium, which means that both, fiber and the leuko dye form, have the negative charge and no mutual affinity. Consequently, dyeing of polyamide fibers with vat/indigoid dyes by standard procedures is not possible.
  • a subject of the present invention it is to solve the problem of indigo reduction without the aforementioned disadvantages and in an ecologically advantageous manner.
  • this goal is achieved by a process for dyeing of cellulose and polyamide-based textile material with indigo which comprises using an aqueous solution of leuco indigo prepared by reductase enzymes and an appropriate redox mediator and, after the leuco indigo has penetrated into the textile material, converting it back into the pigment form with air oxidation.
  • the process also allows reuse of NADH-dependent enzymes from the enzyme reduction bath.
  • Indigo (C.I. Vat Blue 1 ) is one of the oldest dyes, which is used for dyeing cellulose textiles, especially for dyeing cotton (popularity of jeans).
  • Indigo is a vat dye which is insoluble in water.
  • indigo is vatted in an alkali medium in a vessel upstream of the dyebath using inorganic reducing agents such as sodium dithionite and thiourea dioxide or organic reducing agents such as hydroxyacetone.
  • vatting indigo with the reducing agents mentioned is in high concentration of sulfate (from about 3500 to 5000 mg/l) and sulphur content which result from the release of sulphide (S 2" ) ions of the indigo wastewater in the case of using sodium dithionite, or high concentration of oxygen-consuming substances (COD values about 8000 mg/l) in the case of hydroxyacetone usage.
  • S 2 sulphide
  • Electrochemical reduction can be achieved by direct and indirect electrochemical reduction.
  • the direct reduction process is based on a reaction mechanism in which an indigo anion radical is formed by a disproportionation reaction between the dye and the leuco dye form, followed by the electrochemical reduction of this radical.
  • the leuco dye is acting as an electron-shuttle between the electrode and the surface of the dye pigment.
  • U.S. Pat. No. 0088926 A1 describes a mediator systems based on mixed metal complexes, used for reducing dyes.
  • WO 90/15182 discloses a dyeing process wherein indigo is added to the dyebath using mediators.
  • reduction to the total amount of indigo necessary for dyeing requires enormous amounts of charge and large electrode surfaces.
  • conducting salt has to be added to the dying solution in major quantities (about 1.5 g/l of NaOH, 30 g/l Na 2 SO 4 ) to ensure adequate electrical conductivity and hence to minimize the resistance losses and also electrode surface area. This in turn leads to undesirably high levels of sulfate in the dyehouse waste water.
  • Clostridium isatidis unique indigo-reducing bacterium isolated from a woad dye vat that could be employed in a biotechnological indigo-reduction process.
  • the mechanism of bacterial indigo reduction remains unknown, but the unique features of the indigo- reducing C. isatidis indicate possible mechanisms for biotechnological indigo- reduction process.
  • vat and indigoid dyes are confined to the cellulose fibres, and only little attention has been paid to the application of vat/indigoid dyes on other natural (wool, silk, etc.) and especially synthetic fibres.
  • vat/indigoid dyes on other natural (wool, silk, etc.) and especially synthetic fibres.
  • U.S. Pat. No. 2007/0107144 A1 and WO 2007/000775 A2 about indigo dyeing of wool, silk and their blends, where reducing agent employed is sodium dithionite.
  • PA6 [-HN-(CH 2 ) 5 -CO-] n
  • PA6.6 [-HN-(CH 2 ) 6 - NHCO-(CH 2 ) 4 -CO-]n
  • PA is positively charged through absorption of hydrogen ions (NH 2 -PA-COO " * ⁇ HOOC-PA-
  • anionic dyes such as acid, metal complex, direct and reactive dyes.
  • Dyeing of cellulose and polyamide-based textile materials is carried out with leuko indigo obtained by enzymatic reduction of indigo in the presence of a redox mediator followed by penetration into the textile material and converting it back into the pigment form with air oxidation.
  • a dyebath for dyeing of cellulose and polyamide materials is prepared with indigo pigments being mixed reductase (e.g. NADH-dependent from Bacillus subtilis enzymes in presence of NADH) and a mediator (e.g. 1 ,8-dihydroxy-9,10-anthraquinone) causing the indigo particles to become negatively charged.
  • reductase e.g. NADH-dependent from Bacillus subtilis enzymes in presence of NADH
  • a mediator e.g. 1 ,8-dihydroxy-9,10-anthraquinone
  • the dye liquor which comprises the polyamide material, used in the method of the present invention may have a material - liquor ratio in the range from about 1 :5 to about 1 :120, preferably from about 1 :50 to about 1 :80.
  • the dye bath comprises:
  • NADH ⁇ -Nicotinamide adenine dinucleotide disodium salt
  • Used reductase enzymes are active at pH in the range from about 7.0 to about 12.0, preferably from 8.0 to about 10.0. Enzymes exhibit good thermostability as well as good stability towards commonly used dyeing additives such as non-ionic, cationic, or anionic surfactants, salts, polymers, etc. Enzymes with reductase activity are wide-spread in nature and maybe from bacteria such as Bacillus sp. or Escherichia coli or eukaryotic organisms.
  • the enzymatic reduction system comprises one or more chemical mediator agents which enhance the activity of the enzyme exhibiting reductases activity.
  • chemical mediator is defined herein as a chemical compound which acts as a redox mediator to effectively shuttle electrons between the enzyme exhibiting reductases activity and the dye.
  • the chemical mediator may be anthraquinone compound, for example, 1 ,8- dihydroxy-9,10-anthraquinone.
  • the chemical mediator may also be 9,10- anthraquinone-2,6-disulfonic acid disodium salt or 9,10-anthraquinone-2-sulfonic acid sodium salt.
  • the cellulose and polyamide materials to be dyed may be in the form of fibres, yarn, woven or knitted cloth, or finished articles of clothing.
  • this material is prepared by wetting treatment in distillated water for 30 to 60 minutes, preferably from about 30 to about 40 minutes at room temperature, preferably at about 30 0 C to about 50 0 C.
  • the leuco dye adsorption and diffusion step in a dyeing process can be performed at a temperature in the range from about 40 0 C to about 65°C, preferably from about 5O 0 C to about 60 0 C, and at pH in the range of about 7 to about 11 , preferably from about 8 to about 10 for a period of about 60 minutes to about 120 minutes, preferably from about 80 minutes to about 100 minutes.
  • an oxidation process is applied to return the indigo dye in its leuco state to its blue pigment form. Oxidation may be accomplished in several ways. For example, dyed textile material can be passed through air and oxidized with oxygen or oxidizing agent such as hydrogen peroxide can be added in the dyeing bath or in separate oxidizing bath.
  • dyed textile material is dipped into the bath with soaping agent. Soaping is performed at boiling temperature 15 minutes for cellulose fabric and 30 minutes for polyamide fabric to improve the colour fastness and to remove precipitated dye and mediator. Then, the material is rinsed with plain water at 25°C, before being dried on the air.
  • Knitted PA6.6 and woven PA6 pre-wetted for 30 minutes in distillated water at room temperature was dyed in indigo solution in the laboratory dyeing aperture. During its application to the textile material, the dyestuff was reduced to the water- soluble form by means of a NADH-dependent from Bacillus subtilis enzymes in presence of NADH. Process was carried out in TRIS/HCI buffer system, pH 7, at 60 0 C (starting from about 25°C) for at least one hour. The material - liquor ratio was 1 :80.
  • Buffer TriS/HCI, pH 7
  • Na 2 S 2 O 4 solution (1g/L Na 2 S 2 O 4 ) was used as the reducing agent in a comparative test. After the dyeing, 30% of H 2 O 2 (1 :100 diluted) as oxidizing agent was added in the same bath for 5 minutes, and then rinse with the distillated water.
  • Sodium metasilicate-5-hydrate (Cotoblanc) was used for the soaping step. Samples were soaped with 2 g/l Cotoblanc at boiling point for 30 minutes and rinse with plain water for 15 minutes. During soaping the isolated molecules of indigo pigments reorient and associate into a more crystalline form, often producing a significantly different shade along with improved fastness to light and washing. Soaping should also remove any remaining leuco dye and surface dye.
  • the ISO 105-E04 (Part E04) Standard Perspiration fastness was followed. Dyed specimens (4 cm x 10 cm) were placed between two adjacent fabrics and sew along to form a composite specimen. The composites were treated in a standard prepared alkaline and acid solution for 30 minutes at room temperature with 50:1 liquor ratio. After drained, the composites were placed between two plates under a specified pressure in a testing device for 4 hour at 37°C. Removed composite specimens were rinsed with water and dried at air. Colour changes in the specimens and the adjacent fabric were assessed using the Gray Scale method.
  • Fastness testing attests to the resistance of a dyed material against influences during textile production (production usability) and during the use of the textile (wear usability). Fastness to washing, perspiration, as well as light fastness, of the reducing agents used in accordance with the invention must be graded "good” and considered to be comparable to those obtained with the classical chemical (i.e. sodium dithionite) procedure.
  • Table 1 displays the CIEL * a * b* colour values of both, Na2S 2 ⁇ 4 and enzyme (at pH 7) indigo dyed polyamide materials before and after soaping. It is evident that when compared CIEL*a*b* data of both dyeing procedures before and after soaping, the value L * increases after soaping, which indicate on the removal of remaining leuco dyes and surface adsorbed dyes, and consecutive results to brighter colour. With the soaping also decreases the values a* and b*, which indicates on decreasing of the green and blue colour portion.
  • Table 1 shows CIEL*a * b * colour values of differently indigo dyed PA6 in PA6,6 samples at pH 7.
  • Table 2 shows wash, perspiration and light fastness of both, chemically and enzymatically, indigo dyed PA6 and PA6.6 materials at pH 7 after soaping
  • Table 2 displays the wash, perspiration and light fastness of both, chemically (with Na 2 S 2 O 4 ) and enzymatically (at pH 7), indigo reduced and dyed polyamide materials after soaping and rinsing. Wash fastnesses of chemically dyed polyamide materials are slightly better compared with the enzymatically dyed polyamide. There are also differences between PA6 and PA6.6: PA6 possess better wash fastness both chemically and enzymatically dyed compared with PA6,6 material. Perspiration fastnesses of all dyed polyamide materials are excellent for both, alkaline and acid perspiration. Light fastnesses of chemical and enzymatic dyeings are comparable.
  • Knitted PA6.6 and woven PA6 pre-wetted for 30 minutes in distillated water at room temperature was dyed in indigo solution in the laboratory dyeing aperatus. During its application to the textile material, the dyestuff was reduced to the water- soluble form by means of a NADH-dependent enzyme / mediator reducing system. The process was carried out in TRIS/NaOH buffer system, pH 10, at 60 0 C (starting from about 25°C) for at least one hour. The material - liquor ratio was 1 :80.
  • NADH ⁇ -Nicotinamide adenine dinucleotide disodium salt
  • Buffer TriS/NaOH, pH 10
  • Na 2 S 2 O 4 solution (1g/L Na 2 S 2 O 4 ) was used as the reducing agent in a comparative test. After the dyeing, 30% of HbO 2 (1 :100 diluted) as oxidizing agent was added in the same bath for 5 minutes, and then rinse with the distillated water.
  • Sodium metasilicate-5-hydrate (Cotoblanc) was used for the soaping step. Samples were washed with 2 g/l Cotoblanc at boiling point for 30 minutes and rinse with plain water for 15 minutes. During soaping the isolated molecules of indigo pigments reorient and associate into a more crystalline form, often producing a significantly different shade along with improved fastness to light and washing. Soaping should also remove any remaining leuco dye and surface dye.
  • Table 3 displays the CIEL * a * b* data of both chemically (Na 2 S 2 O 4 ) and enzymatic (at pH 10) indigo dyed polyamide materials before and after the soaping.
  • CIEL * a * b* data changes are similar to those obtained at pH 7.
  • Enzymatic dyeing at pH 10 is better in the case of PA6 material used and worse in the case of PA6.6 material comparable to sodium dithionite dyed materials, although the enzymatic dyeing at pH 10 of both materials are more effective than those at pH 7.
  • Table 3 shows CIEL * a*b* colour values of differently indigo dyed PA6 in PA6,6 samples at pH 10.
  • Table 4 shows wash, perspiration and light fastness of both, chemically and enzymatically, indigo dyed PA6 and PA6.6 materials at pH 10 after soaping.
  • wash fastnesses of chemically dyed PA6 materials are similar with enzymatically dyed PA6, meanwhile chemically dyed PA6.6 has better wash fastnesses as enzymatically dyed PA6.6.
  • Perspiration fastnesses for both, alkaline and acid perspiration, of chemically and enzymatic dyed polyamide materials are excellent.
  • Light fastnesses of chemically dyed materials are better as enzymatic dyed, but still comparable.
  • Woven cotton pre-wetted for 30 minutes in distillated water at room temperature was dyed in indigo solution in the laboratory dyeing aperture. During its application to the textile material, the dyestuff was reduced to the water-soluble form by means of a NADH-dependent enzyme / mediator reducing system. Process was carried out in TRIS/HCI buffer system, pH 7, at 60 0 C (starting from about 25°C) for 90 min. The material - liquor ratio was 1 :80.
  • Sodium metasilicate-5-hydrate (Cotoblanc) was used for the soaping step. Samples were washed with 2 g/l Cotoblanc at boiling point for 15 minutes and rinse with plain water for 15 minutes. During soaping, the isolated molecules of indigo pigments reorient and associate into a more crystalline form, often producing a significantly different shade along with improved fastness to light and washing. Soaping should also remove any remaining leuco dye and surface dye.
  • wash fastness properties evaluation The ISO 105-C01 Standard Wash Fastness to Laundering Test method 1 (40 0 C, 30 min) was followed. Dyed specimens (4 cm * 10 cm) were placed between two adjacent fabrics and sew along to form a composite specimen. The composites were treated in 5 g of standard prepared soap and 5 g of anhydrous sodium carbonate per litre of distilled water with ten non-corrodible (stainless) steel balls for 30 minutes at 95°C with 50:1 liquor ratio. Removed composite specimens were rinsed with water and dried at air. Colour changes in the specimens and the adjacent fabric were assessed using the Gray Scale method.
  • Light fastness properties evaluation Light fastness was measured following the ISO 150 B04 standard. Dyed specimens (4 cm * 10 cm) were stapled to the black side of test mask. The mask was placed in a XENOTEST 150S (No. 55007101 , Heraeus) and exposed to a Xenon light source at an irradiance of 1154 W/m 2 for 15 hours. Colour changes in the specimens were assessed using the Blue Scale method.
  • Fastness testing attests to the resistance of a dyed material against influences during textile production (production usability) and during the use of the textile (wear usability). Fastness to washing, perspiration, as well as light fastness, of the reducing agents used in accordance with the invention must be graded "good” and considered to be comparable to those obtained with the classical chemical (i.e. sodium dithionite) procedure.
  • Table 5 displays the CIEL * a * b* data of both chemically (Na 2 SaO 4 ) and enzymatic (at pH 7) indigo dyed cotton materials before and after the soaping. It is evident that when compared CIEL*a*b* data of both dyeing procedures before and after soaping, the value L* increases after soaping, which indicates the removal of remaining leuco dyes and surface adsorbed dyes, and consecutive results to brighter colour. With soaping, the values a* and b* decreases, which indicates on decreasing of the green and blue colour portion, except in the case of enzymatic dyeing, where value b * increase; blue colour portion is increase. In the case of enzymatic dyeing also increase chrome (C*) and hue (h) from 239.4 to 252.68 (shifting to blue).
  • Table 6 shows wash, perspiration and light fastness of both, chemically and enzymatically, indigo dyed cotton materials at pH 7 after soaping
  • Table 6 displays the wash, perspiration and light fastness of cotton samples dyed with either, chemically (with Na 2 S 2 O 4 ) and enzymatically (at pH 7) reduced indigo and after soaping and rinsing. Wash fastness of chemical dyed cotton samples are a bit better comparison with enzymatic dyed one. Perspiration fastnesses of all dyed cotton samples are excellent for both, alkaline and acid perspiration. Light fastnesses of chemical and enzymatic dyeings are comparable.
  • Woven cotton pre-wetted for 30 minutes in distillated water at room temperature was dyed in indigo solution in the laboratory dyeing aperture. During its application to the textile material, the dyestuff was reduced to the water-soluble form by means of a NADH-dependent enzyme / mediator reducing system. The process was carried out in TRIS/HCI buffer system, pH 9, at 60 0 C (starting from about 25°C) for 90 min. The material - liquor ratio was 1 :80.
  • NADH ⁇ -Nicotinamide adenine dinucleotide disodium salt
  • Sodium metasilicate-5-hydrate (Cotoblanc) was used for the soaping step. Samples were washed with 2 g/l Cotoblanc at boiling point for 15 minutes and rinse with plain water for 15 minutes. During soaping the isolated molecules of indigo pigments reorient and associate into a more crystalline form, often producing a significantly different shade along with improved fastness to light and washing. Soaping should also remove any remaining leuco dye and surface dye.
  • Table 7 displays the CIEL * a*b* data of cotton materials dyed with either chemically (Na 2 S 2 O 4 ) and enzymatically (at pH 9) reduced indigo before and after the soaping.
  • CIEL * a * b * changes are similar to those obtained at pH 7.
  • L* values are a bit smaller than those at pH 7 for enzymatic dyeing, but still comparable to chemical dyeing.
  • value a* is decreased, but still higher comparable to chemical dyeing.
  • Hue (h) is increased from 235.33 to 254.46, indicates shifting to blue axle.
  • Table 8 shows wash, perspiration and light fastness of both, chemically (Na 2 S 2 O 4 ) and enzymatically, indigo dyed cotton materials at pH 9 after soaping and rinsing.
  • Wash fastness properties of chemical dyed cotton material are similar to enzymatic dyed samples. Perspiration fastnesses (alkaline and acid) of all dyed cotton samples are excellent. Wash fastness properties of enzymatic dyeing at pH 9 are improved with comparison at pH 7.
  • Woven cotton pre-wetted for 30 minutes in distillated water at room temperature was dyed in indigo solution in the laboratory dyeing aperatus. During its application to the textile material, the dyestuff was reduced to the water-soluble form by means of a NADH-dependent enzyme / mediator reducing system. The process was carried out in TRIS/NaOH buffer system, pH 11 , at 60 0 C (starting from about 25°C) for 90 min. The material - liquor ratio was 1 :80.
  • Dyeing/reduction bath was as follows: - 0.3% indigo on the dry weight of the fabric
  • NADH ⁇ -Nicotinamide adenine dinucleotide disodium salt
  • Sodium metasilicate-5-hydrate (Cotoblanc) was used for the soaping step. Samples were washed with 2 g/l Cotoblanc at boiling point for 15 minutes and rinse with plain water for 15 minutes. During soaping the isolated molecules of indigo pigments reorient and associate into a more crystalline form, often producing a significantly different shade along with improved fastness to light and washing. Soaping should also remove any remaining leuco dye and surface dye.
  • Table 9 displays the CIEL*a*b * data of both chemically (Na 2 S 2 O 4 ) and enzymatic (at pH 11 ) indigo dyed cotton materials before and after the soaping.
  • CIEL*a*b* values of chemical and enzymatic dyeings are comparable.
  • the levelness of the colour shade at pH 11 is better with comparison at pH 7 and 9.
  • Table 10 shows wash, perspiration and light fastness of both, chemically (Na 2 S 2 O 4 ) and enzymatically, indigo dyed cotton materials at pH 11 after soaping and rinsing.
  • R is the reflectance of the fibre at the wavelength of maximum absorption (650 nm).
  • Picture 1 shows K/S values indigo dyed cotton samples with repeated reused enzymatic reduction bath at pH 7, 9 and 11. Reusing of enzymatic reduction bath is possible for five and more repetitions at pH 11 , three repetitions at pH 9 and two repetitions at pH 7. Decreased colour depth at pH 7 can be associated with decreased enzymes activity at acid-neutral pH. At pH 9 and 11 colour depth is increased with every repetition, which is result of addition of new concentration of indigo in dye bath with residue unexhausted dye.
  • the enzyme based reduction bath is capable repeatedly reduce new indigo concentration at pH 9 and 11.
  • NADH ⁇ -Nicotinamide adenine dinucleotide disodium salt
  • Sodium metasilicate-5-hydrate (Cotoblanc) was used for the soaping step. Samples were washed with 2 g/l Cotoblanc at boiling point for 15 minutes and rinse with plain water for 15 minutes. During soaping the isolated molecules of indigo pigments reorient and associate into a more crystalline form, often producing a significantly different shade along with improved fastness to light and washing. Soaping should also remove any remaining leuco dye and surface dye.
  • R is the reflectance of the fibre at the wavelength of maximum absorption (650 nm).
  • Picture 2 shows K/S values indigo dyed PA6.6 samples with repeated reused enzymatic reduction bath at pH 7, 9 and 11. Reusing of enzymatic reduction bath is possible for five and more repetitions at pH 9 and 11. Decreased colour depth at pH 7 can be associated with decreased enzymes activity at acid-neutral pH. At pH 9 and 11 colour depth is increased with every repetition, which is result of addition of new concentration of indigo in dye bath with residue unexhausted dye. Enzymatic reduction bath is capable repeatedly reduce new indigo concentration at pH 9 and 11.
  • Picture 3 shows K/S values indigo dyed PA6 samples with repeated reused enzymatic reduction bath at pH 7, 9 and 11.

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Abstract

La présente invention concerne un procédé respectueux de l'environnement de teinture à l'indigo (C.I. Vat Blue 1) de matériaux textiles contenant de la cellulose et du polyamide, procédé offrant la possibilité de réutiliser (au moins trois fois) le bain de teinture ayant subi une réduction enzymatique. Le procédé de teinture de matériaux textiles à base de cellulose et de polyamide impliquant de l'indigo ayant subi une réduction enzymatique comprend les étapes consistant à soumettre les échantillons de cellulose ou de polyamide au bain de teinture indigo contenant des réductases (par exemple des enzymes dépendant du NADH de Bacillis subtilis en présence d'un médiateur redox, comme la 1,8-dihydroxy-9,10-anthraquinone), puis à une oxydation grâce à l'air, à des enzymes de type oxydases ou à un agent oxydant (par exemple le peroxyde d'hydrogène) après la diffusion du leuco-indigo dans le tissu et, finalement, à un savonnage et à un lavage.
PCT/SI2008/000054 2007-10-18 2008-10-17 Procédé de teinture de matériaux textiles à base de cellulose et de polyamide faisant appel à de l'indigo réduit par des enzymes WO2009051569A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SI200700264A SI22629A (sl) 2007-10-18 2007-10-18 Postopek barvanja poliamidnih tekstilnih materialov z encimsko reduciranim indigom
SIP-200700264 2007-10-18
SI200800219A SI22867A (sl) 2008-09-18 2008-09-18 Postopek ponovne uporabe encimsko redukcijske kopeli za barvanje bombažnih tekstilnih materialov zindigo barvilom
SIP-200800219 2008-09-18

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WO2009051569A2 true WO2009051569A2 (fr) 2009-04-23
WO2009051569A3 WO2009051569A3 (fr) 2009-11-19

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153318A1 (fr) 2011-05-12 2012-11-15 Centi - Centro De Nanotecnologia E Materiais Técnicos Funcionais E Inteligentes Procédé de coloration de matières avec des colorants naturels et articles correspondants
WO2014032134A1 (fr) 2012-08-30 2014-03-06 Cargill, Incorporated Préparation de sucre concentré utilisée en tant qu'agent de réduction de colorants soufrés
WO2021013371A1 (fr) * 2019-07-22 2021-01-28 Sanko Tekstil Isletmeleri San. Ve Tic. A.S. Procédé de teinture de textiles
CN115679718A (zh) * 2022-11-07 2023-02-03 东华大学 一种靛蓝非还原渗染法上染棉纱的方法

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO2012153318A1 (fr) 2011-05-12 2012-11-15 Centi - Centro De Nanotecnologia E Materiais Técnicos Funcionais E Inteligentes Procédé de coloration de matières avec des colorants naturels et articles correspondants
WO2014032134A1 (fr) 2012-08-30 2014-03-06 Cargill, Incorporated Préparation de sucre concentré utilisée en tant qu'agent de réduction de colorants soufrés
WO2021013371A1 (fr) * 2019-07-22 2021-01-28 Sanko Tekstil Isletmeleri San. Ve Tic. A.S. Procédé de teinture de textiles
CN114222841A (zh) * 2019-07-22 2022-03-22 尚科纺织企业工业及贸易公司 纺织品染色工艺
CN114222841B (zh) * 2019-07-22 2024-04-12 尚科纺织企业工业及贸易公司 纺织品染色工艺
CN115679718A (zh) * 2022-11-07 2023-02-03 东华大学 一种靛蓝非还原渗染法上染棉纱的方法
CN115679718B (zh) * 2022-11-07 2024-04-09 东华大学 一种靛蓝非还原渗染法上染棉纱的方法

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