WO2001004409A1 - Dyeing process with sulfur dyes - Google Patents

Dyeing process with sulfur dyes Download PDF

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Publication number
WO2001004409A1
WO2001004409A1 PCT/IB2000/000937 IB0000937W WO0104409A1 WO 2001004409 A1 WO2001004409 A1 WO 2001004409A1 IB 0000937 W IB0000937 W IB 0000937W WO 0104409 A1 WO0104409 A1 WO 0104409A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
dyeing
process according
polyamide
substrate
Prior art date
Application number
PCT/IB2000/000937
Other languages
French (fr)
Inventor
Marcos Furrer
Oskar Annen
Original Assignee
Clariant Finance (Bvi) Limited
Clariant International Ltd.
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Filing date
Publication date
Application filed by Clariant Finance (Bvi) Limited, Clariant International Ltd. filed Critical Clariant Finance (Bvi) Limited
Priority to BR0012389-7A priority Critical patent/BR0012389A/en
Priority to KR1020027000331A priority patent/KR20020027484A/en
Priority to JP2001509800A priority patent/JP2003504532A/en
Priority to EP00939011A priority patent/EP1200669A1/en
Priority to MXPA02000423A priority patent/MXPA02000423A/en
Publication of WO2001004409A1 publication Critical patent/WO2001004409A1/en

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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
    • 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
    • D06P1/30—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 sulfur dyes
    • 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
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8209—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing amide groups

Definitions

  • This invention comprises a process for dyeing polyamide substrates or polyamide-containing substrates with sulfur dyes and substrates dyed with such a dye.
  • Sulfur dyes are an important class of dyes. This class is extensively described in Venkatamaran "The Chemistry of Synthetic Dyes", volume II (chapters XXXV and XXXVI) (1952) and volume VII (1974) and in the Colour Index. Essentially they are dyes which contain aromatically attached oligo sulfur linkages which are reducible to thiol groups and which may be of oligomeric or polymeric structure. They are mainly obtained by thionation of the respective intermediates at high temperature, for example above 100°C, especially in the temperature range from 1 10 to 300°C (eg by baking or in the melt or in the presence of water and/or an inert organic solvent).
  • Sulfur dyes are most prominently used in cellulose dyeing.
  • the most widely used sulfur dye of this category is C.I. Sulfur Black 1 , which is based on the organic compound I.
  • sulfur dyes include CI. Sulfur Black 2, CI. Sulfur Black 1 1 , CI. Sulfur Black 18, CI. Sulfur Green 35, etc. A detailed list may be found in the Colour Index.
  • sulfur dyes are used in particular to dye cellulose or cellulose- containing fabric.
  • the most widely used process for dyeing these materials is the exhaust and continuous process.
  • Sulfur dyes are preferably used in aqueous form, especially in the form of an aqueous paste.
  • the aqueous form may be prepared, for example, by suspending a commercially available sulfur dye, or a sulfur dye prepared by baking or in the melt, in water.
  • Sulfur dyes are applied to the substrates in the reduced (leuco) form and are then oxidized. That is, sulfur dyes may be added to the dyeing liquor in the reduced form or in the oxidized form, which is then reduced using a suitable reducing agent.
  • Useful reducing agents are .all reducing agents known as suitable in the prior art, especially sodium hydrosulfide, sodium formaldehydesulfoxylate, potassium formaldehydesulfoxylate, zinc formaldehydesulfoxylate, thiourea, polysulfides (Na x S y ), sodium sulfide, hydroxyacetone and glucose.
  • Useful oxidizing agents include all oxidizing agents known as suitable in the prior art, especially bichromates (K 2 Cr0 7 . Na 2 CrO ), bromates (NaBr0 3 , NaI0 3 ), bromites (NaBr0 2 ), perborates ( aB0 3 ), persulfates ( 2 S 2 0 8 , Na 2 S 2 O 8 ), hydrogen peroxide and chlorates (NaClO 3 ).
  • Polyamide substrates and polyamide-containing substrates have hitherto not been satisfactorily dyeable with certain sulfur dyes, for example C.I. Sulfur Black 1 or CI. Sulfur Black 2.
  • sulfur dyes for example C.I. Sulfur Black 1 or CI. Sulfur Black 2.
  • polyamide/cotton blends were not dyeable on-tone with just one dye.
  • polyamide substrates or polyamide-containing substrates for example polyamide/Lycra ® , polyamide/cotton, polyamide/cotton/Lycra ® (Lycra ® is a trademark of DuPont), polyamide/cotton, etc, to be dyed with Sulfur Black 1, Sulfur Black 2 or Sulfur Green 16 in good fastnesses.
  • Polyamide microfibers for example Meryl ® (Meryl ® is a trademark of Nylstar) are likewise suitable for dyeing according to the invention.
  • a further advantage of the process according to the invention is that good on-tone dyeing is obtained with just one dye and a one-step dyeing process, for example on a cotton/polyamide substrate, and this is something previously known processes did not provide.
  • polyamides and polyamide-containing substrates are dyed with individual sulfur dyes at up to 95°C and a pH of 12 - 14.
  • the sulfur dyes used may be used not only in reduced form but also in oxidized form.
  • the process of the invention is particularly suitably carried out using dyes of the Diresul ® EV type.
  • Diresul ® is a trademark of Clariant.
  • the liquor ratio used in the examples hereinbelow is always 10: 1 , unless otherwise stated.
  • the substrate has very good fastnesses.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Black EV-4G (C.I. Sulfur Black 1 )
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 3 g/1 of calcined sodium carbonate, l ml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate.
  • the polyamide substrate (PA 6.6 Nylsuisse Art.2044) is introduced into the dyeing liquor at 60°C.
  • the dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min.
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate has good fastnesses.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate has good fastnesses.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Olive RDT-B liq. (C.I. Sulfur Green 16) (manufactured by Clariant), 3 g/1 of calcined sodium carbonate, lml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate.
  • the polyamide substrate (PA 6.6 Nylsuisse Art.2044) is introduced into the dyeing liquor at 60°C
  • the dyeing liquor is then heated to 95°C at 2°C/min.
  • Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min.
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate has good fastnesses.
  • the aqueous dyeing liquor is made up of 20% of Diresul ® Black EV-PL (C.I. Sulfur Black 2) (manufactured by Clariant), 3g/l of calcined sodium carbonate, 1 ml/1 of a wetting agent and introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 1 10°C at
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate has good fastnesses.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 3g/l of calcined sodium carbonate, lml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate.
  • the polyamide/Lycra (80:20) blend substrate is introduced into the dyeing liquor at 60°C
  • the dyeing liquor is then heated to 95°C at 2°C/min.
  • Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min.
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate has good fastnesses.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 20g l of calcined Glauber salt, 3g/l of calcined sodium carbonate, lml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate.
  • the polyamide/cotton/Lycra (30:60: 10) blend substrate is introduced into the dyeing liquor at 60°C
  • the dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min.
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate shows excellent equalization in color strength and hue between the cotton and the polyamide and has commercially acceptable fastnesses.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Black EV-4G (CI. Sulfur Black 1 ) (manufactured by Clariant), 20g/l of calcined Glauber salt, 3g/l of calcined sodium carbonate, lml/1 of a wetting agent and 5 g/1 of sodium formaldehydesulfoxylate.
  • the polyamide/cotton Lycra ® (30:60: 10) blend substrate is introduced into the dyeing liquor at 60°C
  • the dyeing liquor is then heated to 1 10°C at 2°C/min. Dyeing continues at 1 10°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min.
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate shows excellent equalization in color strength and hue between the cotton and the polyamide and has commercially acceptable fastnesses.
  • the aqueous dyeing liquor is made up of 15% of Diresul ® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 3g/l of calcined sodium carbonate, l ml/1 of a wetting agent and 5 g/1 of sodium formaldehydesulfoxylate.
  • the polyamide/Lycra ® (80:20) blend substrate is introduced into the dyeing liquor at 60°C
  • the dyeing liquor is then heated to 95°C at 2°C/min.
  • Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min.
  • the pH is between 9 and 10.5 during the dyeing process.
  • the substrate is then rinsed with hot and cold water.
  • the dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
  • the substrate is then rinsed with hot and cold water.
  • the substrate has good fastnesses.

Abstract

A process for dyeing polyamide or polyamide-containing substrates with sulfur dyes comprises effecting said dyeing in a pH range of 8 - 11 and at 90 - 120 °C and with reducing agents which are suitable under these conditioners. Also claimed are substrates dyed using this process.

Description

Dyeing Process with Sulfur Dyes
This invention comprises a process for dyeing polyamide substrates or polyamide-containing substrates with sulfur dyes and substrates dyed with such a dye.
Sulfur dyes are an important class of dyes. This class is extensively described in Venkatamaran "The Chemistry of Synthetic Dyes", volume II (chapters XXXV and XXXVI) (1952) and volume VII (1974) and in the Colour Index. Essentially they are dyes which contain aromatically attached oligo sulfur linkages which are reducible to thiol groups and which may be of oligomeric or polymeric structure. They are mainly obtained by thionation of the respective intermediates at high temperature, for example above 100°C, especially in the temperature range from 1 10 to 300°C (eg by baking or in the melt or in the presence of water and/or an inert organic solvent). The exact structure of sulfur dyes is generally unknown or incompletely known, even though the starting materials are known, since, for example, the number or position of the oligo sulfur linkages, the number of sulfur atoms in an oligo sulfur linkage, the number of hetero rings and/or NH linkages and/or the number of structural repeat units in the sulfur dye molecule may vary according to starting materials and synthetic conditions.
Sulfur dyes are most prominently used in cellulose dyeing. The most widely used sulfur dye of this category is C.I. Sulfur Black 1 , which is based on the organic compound I.
Figure imgf000002_0001
Other sulfur dyes include CI. Sulfur Black 2, CI. Sulfur Black 1 1 , CI. Sulfur Black 18, CI. Sulfur Green 35, etc. A detailed list may be found in the Colour Index.
As mentioned above, sulfur dyes are used in particular to dye cellulose or cellulose- containing fabric. The most widely used process for dyeing these materials is the exhaust and continuous process. Sulfur dyes are preferably used in aqueous form, especially in the form of an aqueous paste.
The aqueous form may be prepared, for example, by suspending a commercially available sulfur dye, or a sulfur dye prepared by baking or in the melt, in water.
Sulfur dyes are applied to the substrates in the reduced (leuco) form and are then oxidized. That is, sulfur dyes may be added to the dyeing liquor in the reduced form or in the oxidized form, which is then reduced using a suitable reducing agent.
It is customary to use the reducing agent in excess to ensure that the dyes are indeed present in the reduced form, since atmospheric oxygen, for example, can oxidize sulfur dyes.
Useful reducing agents are .all reducing agents known as suitable in the prior art, especially sodium hydrosulfide, sodium formaldehydesulfoxylate, potassium formaldehydesulfoxylate, zinc formaldehydesulfoxylate, thiourea, polysulfides (NaxSy), sodium sulfide, hydroxyacetone and glucose.
Useful oxidizing agents include all oxidizing agents known as suitable in the prior art, especially bichromates (K2Cr07. Na2CrO ), bromates (NaBr03, NaI03), bromites (NaBr02), perborates ( aB03), persulfates ( 2S208, Na2S2O8), hydrogen peroxide and chlorates (NaClO3).
Polyamide substrates and polyamide-containing substrates have hitherto not been satisfactorily dyeable with certain sulfur dyes, for example C.I. Sulfur Black 1 or CI. Sulfur Black 2. For instance polyamide/cotton blends were not dyeable on-tone with just one dye.
The present invention, then, allows polyamide substrates or polyamide-containing substrates, for example polyamide/Lycra®, polyamide/cotton, polyamide/cotton/Lycra® (Lycra® is a trademark of DuPont), polyamide/cotton, etc, to be dyed with Sulfur Black 1, Sulfur Black 2 or Sulfur Green 16 in good fastnesses. Polyamide microfibers, for example Meryl® (Meryl ® is a trademark of Nylstar) are likewise suitable for dyeing according to the invention.
A further advantage of the process according to the invention is that good on-tone dyeing is obtained with just one dye and a one-step dyeing process, for example on a cotton/polyamide substrate, and this is something previously known processes did not provide. In the prior art, polyamides and polyamide-containing substrates are dyed with individual sulfur dyes at up to 95°C and a pH of 12 - 14.
The invention provides a process for dyeing polyamides or polyamide-containing substrates with sulfur dyes and/or mixtures thereof, which comprises effecting said dyeing in a pH range of 7.5 - 1 1, especially 8 - 1 1, and at 60 - 120°C, especially 90 - 120°C
The sulfur dyes used may be used not only in reduced form but also in oxidized form.
Preference is given to a process of the invention wherein CI. Sulfur Black 1, CI. Sulfur Black 2, CI. Sulfur Green 16 and/or mixtures thereof are used as sulfur dye.
Particular preference is given to a process of the invention wherein CI. Sulfur Black 1 is used as sulfur dye.
Preference is likewise given to a process of the invention wherein the dyeing is effected at 60 - 1 10°C, especially 90 - 1 10°C, more preferably at 95°C, likewise more preferably at 1 10°C
Preference is given to a process of the invention wherein the dyeing is effected at a pH of 9.5 - 11.
Preference is given to a process of the invention wherein sodium formaldehydesulfoxylate, potassium formaldehydesulfoxylate, zinc formaldehydesulfoxylate and/or mixtures thereof are used as reducing agent.
The invention likewise provides a process wherein wetting agents, lubricants, sequestrants and or antifoams are added.
The invention further provides a polyamide or polyamide-containing substrate dyed by a process according to the invention.
The process of the invention is particularly suitably carried out using dyes of the Diresul® EV type. (Diresul® is a trademark of Clariant). .
The examples hereinbelow illustrate the invention. Percentages are by weight, unless otherwise stated. Temperatures are in degrees Celsius.
The liquor ratio used in the examples hereinbelow is always 10: 1 , unless otherwise stated.
Example 1:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black 1 )
(manufactured by Clariant), 5g/l of sodium formaldehydesulfoxylate, 3g/l of calcined sodium carbonate and l ml/1 of a wetting agent. The polyamide microfiber (Meryl®) is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 1 10°C at 2°C/min. Dyeing continues at 1 10°C and pH 9 - 10.5 for 30 minutes, and the bath is then cooled down to 70°C at 2°C/min. The substrate is then rinsed with hot and cold water.
The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water.
The substrate has very good fastnesses.
Example 2:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black 1 )
(manufactured by Clariant), 5 g/1 of sodium formaldehydesulfoxylate, 1 g/1 of calcined sodium carbonate and 1 ml/1 of a wetting agent. The polyamide microfiber (Meryl®) is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 1 10°C at
2°C/min. Dyeing continues at 1 10°C and pH 9 - 10.5 for 30 minutes, and the bath is then cooled down to 70°C at 2°C/min. The substrate is then rinsed with hot and cold water.
The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water.
The substrate has good fastnesses.
Example 3:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 3 g/1 of calcined sodium carbonate, l ml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate. The polyamide substrate (PA 6.6 Nylsuisse Art.2044) is introduced into the dyeing liquor at 60°C. The dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water. The substrate has good fastnesses.
Example 4:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black I ) (manufactured by Clariant), 1 g/1 of calcined sodium carbonate, 1 ml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate. The polyamide substrate (PA 6.6 Nylsuisse Art.2044) is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water. The substrate has good fastnesses.
Example 5:
The aqueous dyeing liquor is made up of 15% of Diresul® Olive RDT-B liq. (C.I. Sulfur Green 16) (manufactured by Clariant), 3 g/1 of calcined sodium carbonate, lml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate. The polyamide substrate (PA 6.6 Nylsuisse Art.2044) is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water. The substrate has good fastnesses.
Example 6:
The aqueous dyeing liquor is made up of 20% of Diresul® Black EV-PL (C.I. Sulfur Black 2) (manufactured by Clariant), 3g/l of calcined sodium carbonate, 1 ml/1 of a wetting agent and introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 1 10°C at
2°C/min. Dyeing continues at 1 10°C for 30 minutes, and the bath is then cooled down to
70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes.
The substrate is then rinsed with hot and cold water.
The substrate has good fastnesses.
Example 7:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 3g/l of calcined sodium carbonate, lml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate. The polyamide/Lycra (80:20) blend substrate is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water. The substrate has good fastnesses.
Example 8:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 20g l of calcined Glauber salt, 3g/l of calcined sodium carbonate, lml/1 of a wetting agent and 5g/l of sodium formaldehydesulfoxylate. The polyamide/cotton/Lycra (30:60: 10) blend substrate is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water. The substrate shows excellent equalization in color strength and hue between the cotton and the polyamide and has commercially acceptable fastnesses. Example 9:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (CI. Sulfur Black 1 ) (manufactured by Clariant), 20g/l of calcined Glauber salt, 3g/l of calcined sodium carbonate, lml/1 of a wetting agent and 5 g/1 of sodium formaldehydesulfoxylate. The polyamide/cotton Lycra® (30:60: 10) blend substrate is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 1 10°C at 2°C/min. Dyeing continues at 1 10°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water.
The substrate shows excellent equalization in color strength and hue between the cotton and the polyamide and has commercially acceptable fastnesses.
Example 10:
The aqueous dyeing liquor is made up of 15% of Diresul® Black EV-4G (C.I. Sulfur Black 1 ) (manufactured by Clariant), 3g/l of calcined sodium carbonate, l ml/1 of a wetting agent and 5 g/1 of sodium formaldehydesulfoxylate. The polyamide/Lycra® (80:20) blend substrate is introduced into the dyeing liquor at 60°C The dyeing liquor is then heated to 95°C at 2°C/min. Dyeing continues at 95°C for 60 minutes, and the bath is then cooled down to 70°C at 2°C/min. The pH is between 9 and 10.5 during the dyeing process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate by using a sodium bromate solution (4g/l) at 70°C and a pH of 3 - 4, adjusted with acetic acid, for 30 minutes. The substrate is then rinsed with hot and cold water. The substrate has good fastnesses.

Claims

What is claimed is:1 A process for dyeing polyamides or polyamide-containing substrates with sulfur dyes and or mixtures thereof, which comprises effecting said dyeing in a pH range of 7 5 - 1 1 and at 60 - 120°C2 A process according to claim 1, wherein the sulfur dyes used are oxidized sulfur dyes which are reduced in the dyeing solution by a reducing agent which is suitable under the conditions indicated in claim 1A process according to claim 1, wherein reduced sulfur dyes are usedA process according to any one of claims 1 - 3, wherein C I Sulfur Black 1, C I Sulfur Black 2, C I Sulfur Green 16 and/or mixtures thereof are used as sulfur dyeA process according to any one of claims 1 - 3, wherein C I Sulfur Black 1 is used as sulfur dyeA process according to any one of claims 1 - 5, wherein said dyeing is effected at 90 - 1 10°CA process according to any one of claims 1 - 8, wherein said dyeing is effected at a pH of 9 5 - 1 1A process according to any one of claims 2, 4, 5, 6 and 7, wherein sodium formaldehydesulfoxylate, potassium formaldehydesulfoxylate, zinc formaldehydesulfoxylate and/or mixtures thereof are used as reducing agentA process according to any one of claims 1 - 8, wherein wetting agents, lubricants, sequestrants and/or antifoams are added0 A polyamide or polyamide-containing substrate dyed by a process according to any one of claims 1 - 9 AMENDED CLAIMS[received by the International Bureau on 24 November 2000 (24.1 1.00); original claims 1 and 4-10 replaced by amended claims 1 and 4-9; remaining claims unchanged (1 page)]
1. A process for dyeing polyamides or polyamide-containing substrates with CI. Sulfur Black 1 , CI. Sulfur Black 2, CI. Sulfur Green 16 and/or
5 mixtures thereof, which comprises effecting said dyeing in a pH range of
7.5 - 11 and at 60 - 120°C
2. A process according to claim 1, wherein the sulfur dyes used are oxidized sulfur dyes which are reduced in the dyeing solution by a reducing agent
10 which is suitable under the conditions indicated in claim 1.
3. A process according to claim 1 , wherein reduced sulfur dyes are used.
4. A process according to any one of claims 1 - 3, wherein CI. Sulfur Black 1 15 is used as sulfur dye.
5. A process according to any one of claims 1 - 4, wherein said dyeing is effected at 90 - 110°C
20 6. A process according to any one of claims 1 - 5, wherein said dyeing is effected at a pH of 9.5 - 11.
7. A process according to any one of claims 2, 4, 5 and 6, wherein sodium formaldehydesulfoxylate, potassium formaldehydesulfoxylate, zinc
25 formaldehydesulfoxylate and/or mixtures thereof are used as reducing agent.
8. A process according to any one of claims 1 - 7, wherein wetting agents, lubricants, sequestrants and/or antifoams are added.
30
9. A polyamide or polyamide-containing substrate dyed by a process according to any one of claims 1 - 8.
SHEET ARTICLE 1ft
PCT/IB2000/000937 1999-07-12 2000-07-11 Dyeing process with sulfur dyes WO2001004409A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR0012389-7A BR0012389A (en) 1999-07-12 2000-07-11 Sulfur dyeing process
KR1020027000331A KR20020027484A (en) 1999-07-12 2000-07-11 Dyeing process with sulfur dyes
JP2001509800A JP2003504532A (en) 1999-07-12 2000-07-11 Coloring method with sulfur dye
EP00939011A EP1200669A1 (en) 1999-07-12 2000-07-11 Dyeing process with sulfur dyes
MXPA02000423A MXPA02000423A (en) 1999-07-12 2000-07-11 Dyeing process with sulfur dyes.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1278/99 1999-07-12
CH127899 1999-07-12

Publications (1)

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WO2001004409A1 true WO2001004409A1 (en) 2001-01-18

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KR (1) KR20020027484A (en)
BR (1) BR0012389A (en)
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WO (1) WO2001004409A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108797155A (en) * 2018-05-16 2018-11-13 佛山大唐纺织印染服装面料有限公司 It is a kind of have wash the whole dyeing technique for taking off style coating denim fabric
EP3536737A1 (en) * 2018-03-08 2019-09-11 Archroma IP GmbH Method for dyeing a plastic object

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR906232A (en) * 1944-08-02 1945-12-27 Ig Farbenindustrie Ag Process for dyeing polyamides and polyurethanes using sulfur dyes
DE818041C (en) * 1948-03-04 1951-10-22 Johann Maria Lanczer Process for dyeing synthetic polyamide and polyester fibers and fabrics made from these fibers
US2904385A (en) * 1956-07-17 1959-09-15 Oreal Dyeing animal fibres and compositions therefor
FR2250848A1 (en) * 1973-11-13 1975-06-06 Cassella Farbwerke Mainkur Ag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR906232A (en) * 1944-08-02 1945-12-27 Ig Farbenindustrie Ag Process for dyeing polyamides and polyurethanes using sulfur dyes
DE818041C (en) * 1948-03-04 1951-10-22 Johann Maria Lanczer Process for dyeing synthetic polyamide and polyester fibers and fabrics made from these fibers
US2904385A (en) * 1956-07-17 1959-09-15 Oreal Dyeing animal fibres and compositions therefor
FR2250848A1 (en) * 1973-11-13 1975-06-06 Cassella Farbwerke Mainkur Ag

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3536737A1 (en) * 2018-03-08 2019-09-11 Archroma IP GmbH Method for dyeing a plastic object
CN108797155A (en) * 2018-05-16 2018-11-13 佛山大唐纺织印染服装面料有限公司 It is a kind of have wash the whole dyeing technique for taking off style coating denim fabric

Also Published As

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EP1200669A1 (en) 2002-05-02
KR20020027484A (en) 2002-04-13
BR0012389A (en) 2002-03-19
JP2003504532A (en) 2003-02-04
MXPA02000423A (en) 2002-07-30

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