EP0181257B1 - Process for the oxidation of sulphur dyestuffs - Google Patents

Process for the oxidation of sulphur dyestuffs Download PDF

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Publication number
EP0181257B1
EP0181257B1 EP19850402090 EP85402090A EP0181257B1 EP 0181257 B1 EP0181257 B1 EP 0181257B1 EP 19850402090 EP19850402090 EP 19850402090 EP 85402090 A EP85402090 A EP 85402090A EP 0181257 B1 EP0181257 B1 EP 0181257B1
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Prior art keywords
oxidation
vanadate
process according
hydrogen peroxide
dye
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EP19850402090
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German (de)
French (fr)
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EP0181257A1 (en
Inventor
Jean Balland
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Manufacture de Produits Chimiques Protex SARL
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Manufacture de Produits Chimiques Protex SARL
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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
    • D06P1/222—Oxidising agents
    • 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

Definitions

  • the present invention relates to an improvement made to the oxidation and fixing of sulfur dyes, or vat dyes.
  • the Applicant has on the other hand experimentally found that the presence in a bath of hydrogen peroxide, of small quantities of a metal salt, such as copper sulphate, quantities insufficient to increase the speed of oxidation and allow the development of the various colors, and simultaneously the presence in the bath of small quantities of a vanadate, makes it possible to quickly oxidize all the colors without having the disadvantage of modifying their tone.
  • a metal salt such as copper sulphate
  • the present invention therefore relates to a process for the oxidation of the dye of a fabric or fiber dyed with a sulfur dye or a vat dye using a solution of hydrogen peroxide in the presence of a salt.
  • vanadate at a pH between 3 and 6 and at a temperature between 20 and 95 ° C, the proportions of hydrogen peroxide and vanadate salt being respectively between 0.1 and 30 g and between 0.05 and 0.5 g per liter of bath, characterized in that the oxidation is carried out in the simultaneous presence of a metal salt chosen from copper, iron, nickel, cobalt and manganese salts, the amount of this salt being between 0.01 and 1 g per liter of oxidizing bath.
  • the oxidation is carried out at temperatures between 40 ° and 60 ° C.
  • the vanadate can be chosen from the family comprising vandates of alkali metals and ammonium vanadate.
  • the amount of hydrogen peroxide will be between 1 g and 5 g of hydrogen peroxide per liter of oxidation bath.
  • the amount of vanadate will preferably be between 0.1 and 0.2 g / l.
  • the amount of the metal salt will preferably be between 0.05 to 0.1 g per liter of bath.
  • all the sulfur dyes or tank dyes can be oxidized whatever the dyeing process, the equipment used or the nature of the dyed fibers.
  • a cotton fabric, previously bleached, is dyed with 10% sulfur red No. 10 (percentage expressed relative to the weight of the fiber).
  • Oxidation is carried out on three separate portions of the f i-dyed fibers and rinsed, using the following baths respectively:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Chemical Treatment Of Metals (AREA)

Description

La présente invention concerne une amélioration apportée à l'oxydation et à la fixation des colorants au soufre, ou colorants de cuve.The present invention relates to an improvement made to the oxidation and fixing of sulfur dyes, or vat dyes.

On sait que l'oxydation, après teinture, des colorants au soufre ou colorants de cuve peut être réalisée à l'aide de différents agents d'oxydation. On peut, par exemple, citer parmi les composés les plus utilisés:

  • - Les chromates ou dichromates des métaux alcalins,
  • - Les composés halogénés des métaux alcalins tels que les bromates, chlorites ou iodates,
  • - Le peroxyde d'hydrogène.
It is known that the oxidation, after dyeing, of the sulfur dyes or tank dyes can be carried out using different oxidizing agents. One can, for example, mention among the most used compounds:
  • - Chromates or dichromates of alkali metals,
  • - Halogenated compounds of alkali metals such as bromates, chlorites or iodates,
  • - Hydrogen peroxide.

Cependant, l'emploi de chromates ou bichromates présente l'inconvénient de provoquer une pollution importante des eaux de rejet. On sait, en outre, que ces composés peuvent modifier de façon, importante la tonalité de certains coloris ou provoquer également une diminution de l'hydro- philité des fibres.However, the use of chromates or dichromates has the drawback of causing significant pollution of the waste water. It is also known that these compounds can significantly modify the tone of certain colors or also cause a decrease in the hydrophilicity of the fibers.

L'emploi des dérivés halogénés est fréquem- ment préconisé, notamment en présence de vanadate alcalin: on sait, toutefois, que ces différents composés sont difficilement utilisables avec certains appareils, tels que le Jigger.The use of halogenated derivatives is frequently recommended, in particular in the presence of alkaline vanadate: it is known, however, that these different compounds are difficult to use with certain devices, such as the Jigger.

L'emploi de peroxyde d'hydrogène est efficace en milieu alcalin mais présente cependant l'inconvénient d'occasioner la suroxydation de nombreux colorants.The use of hydrogen peroxide is effective in an alkaline medium but has the disadvantage of occasioning the overoxidation of many dyes.

Quant à l'emploi de peroxyde d'hydrogène en milieu acide, il ne permet pas d'oxyder l'ensemble des colorants, comme le reconnaît l'article de R. Klein publié dans le Journal of the Society of Dyers and Colourists, vol. 98, N° 4, Avril 1982, pages 106-113, qui passe en revue les différents procédés possibles d'oxydation des colorants au soufre.As for the use of hydrogen peroxide in an acid medium, it does not allow all the dyes to be oxidized, as recognized by the article by R. Klein published in the Journal of the Society of Dyers and Colorists, vol . 98, No. 4, April 1982, pages 106-113, which reviews the various possible processes for the oxidation of sulfur dyes.

On sait que certains métaux sont susceptibles d'activer la décomposition d'une dilution aqueuse de peroxyde d'hydrogène et d'accroître la vitesse de son pouvoir oxydant dans un domaine de pH acide. L'emploi de sels de fer (comme décrit dans EP-A-34005), de nickel ou de cuivre par exemple, tels que le sulfate de cuivre, permet d'activer fortement la décomposition du peroxyde d'hydrogène. Toutefois, une telle oxydation, réalisée par exemple en présence de sels de cuivre, comme décrit dans US-A-4 036 586, entraîne une modification importante des divers coloris. De son côté, FR-A-1 421 707 a proposé d'activer la décomposition du peroxyde d'hydrogène à l'aide de sels de Mg, Ca, Sr ou Ba.It is known that certain metals are capable of activating the decomposition of an aqueous dilution of hydrogen peroxide and of increasing the speed of its oxidizing power in an acid pH range. The use of iron salts (as described in EP-A-34005), nickel or copper for example, such as copper sulphate, makes it possible to strongly activate the decomposition of hydrogen peroxide. However, such an oxidation, carried out for example in the presence of copper salts, as described in US-A-4,036,586, results in a significant modification of the various colors. For its part, FR-A-1 421 707 has proposed to activate the decomposition of hydrogen peroxide using salts of Mg, Ca, Sr or Ba.

D'autre part, l'emploi d'un vanadate dans un bain de peroxyde d'hydrogène, comme décrit dans DE-A-29 14 260, ne permet pas d'accroître suffisamment la vitesse d'oxydation de la solution oxydante.On the other hand, the use of a vanadate in a hydrogen peroxide bath, as described in DE-A-29 14 260, does not allow the rate of oxidation of the oxidizing solution to be increased sufficiently.

La Demanderesse a par contre trouvé expérimentalement que la présence dans un bain de peroxyde d'hydrogène, de faibles quantités d'un sel métallique, tel que du sulfate de cuivre, quantités insuffisantes pour accroître la vitesse d'oxydation et permettre le développement des divers coloris, et simultanément la présence dans le bain de faibles quantités d'un vanadate, permet d'oxyder rapidement tous les coloris sans présenter l'inconvénient de modifier leur tonalité.The Applicant has on the other hand experimentally found that the presence in a bath of hydrogen peroxide, of small quantities of a metal salt, such as copper sulphate, quantities insufficient to increase the speed of oxidation and allow the development of the various colors, and simultaneously the presence in the bath of small quantities of a vanadate, makes it possible to quickly oxidize all the colors without having the disadvantage of modifying their tone.

Comparativement, l'application séparée de quantités identiques de sulfate de cuivre ou de vanadate ne permet pas d'oxyder aussi rapidement l'ensemble des divers colorants. Par contre, l'application simultanée d'un vanadate et d'un sel métallique en présence de peroxyde d'hydrogène permet d'oxyder rapidement l'ensemble des colorants au soufre, quel que soit le procédé de teinture ou l'appareillage considéré.In comparison, the separate application of identical amounts of copper sulphate or vanadate does not allow all the various dyes to be oxidized as quickly. On the other hand, the simultaneous application of a vanadate and a metal salt in the presence of hydrogen peroxide makes it possible to rapidly oxidize all of the dyes with sulfur, whatever the dyeing process or the apparatus considered.

La présente invention a donc pour objet un procédé d'oxydation du colorant d'une étoffe ou fibre teinte avec un colorant au soufre ou un colorant de cuve à l'aide d'une solution de peroxyde d'hydrogène en présence d'un sel vanadate, à un pH compris entre 3 et 6 et à une température comprise entre 20 et 95 °C, les proportions de peroxyde d'hydrogène et de sel vanadate étant comprises, respectivement, entre 0,1 et 30 g et entre 0,05 et 0,5 g par litre de bain, caractérisé en ce que l'oxydation est effectuée en la présence simultanée d'un sel métallique choisi parmi les sels de cuivre, de fer, de nickel, de cobalt et de manganèse, la quantité de ce sel étant comprise entre 0,01 et 1 g par litre de bain oxydant.The present invention therefore relates to a process for the oxidation of the dye of a fabric or fiber dyed with a sulfur dye or a vat dye using a solution of hydrogen peroxide in the presence of a salt. vanadate, at a pH between 3 and 6 and at a temperature between 20 and 95 ° C, the proportions of hydrogen peroxide and vanadate salt being respectively between 0.1 and 30 g and between 0.05 and 0.5 g per liter of bath, characterized in that the oxidation is carried out in the simultaneous presence of a metal salt chosen from copper, iron, nickel, cobalt and manganese salts, the amount of this salt being between 0.01 and 1 g per liter of oxidizing bath.

De préférence, on réalise l'oxydation à des températures comprises entre 40° et 60 °C.Preferably, the oxidation is carried out at temperatures between 40 ° and 60 ° C.

Parmi les sels métalliques utilisables, la préférence est donnée à l'emploi des sels de cuivre, tels que le sulfate de cuivre.Among the metal salts which can be used, preference is given to the use of copper salts, such as copper sulphate.

Le vanadate pourra être choisi dans la famille comprenant les vandates des métaux alcalins et le vanadate d'ammonium.The vanadate can be chosen from the family comprising vandates of alkali metals and ammonium vanadate.

De préférence, la quantité de peroxyde d'hydrogène sera comprise entre 1 g et 5 g de peroxyde d'hydrogène par litre de bain d'oxydation.Preferably, the amount of hydrogen peroxide will be between 1 g and 5 g of hydrogen peroxide per liter of oxidation bath.

La quantité de vanadate sera comprise de préférence entre 0,1 et 0,2 g/I.The amount of vanadate will preferably be between 0.1 and 0.2 g / l.

La quantité du sel métallique sera comprise, de préférence, entre 0,05 à 0,1 g par litre de bain.The amount of the metal salt will preferably be between 0.05 to 0.1 g per liter of bath.

Grâce à l'invention, l'ensemble des colorants au soufre ou colorants de cuve, pourra être oxydé quel que soit le procédé de teinture, l'appareillage retenu ou la nature des fibres teintes.Thanks to the invention, all the sulfur dyes or tank dyes can be oxidized whatever the dyeing process, the equipment used or the nature of the dyed fibers.

Les exemples suivants permettront d'illustrer, de façon non limitative, les possibilités offertes par la présente invention. Dans les exemples ci-après, on utilise le Rouge au soufre n° 10 correspondant dans le Color Index au Numéro 53 228. Ce colorant correspond à l'un des éléments difficilement oxydables et donnant le plus de difficultés au cours de l'oxydation.The following examples will illustrate, without limitation, the possibilities offered by the present invention. In the examples below, use the sulfur red No. 10 corresponding in the Color Index at Number 53 228. This dye corresponds to one of the elements which are difficult to oxidize and which gives the most difficulty during oxidation.

Exemple 1Example 1

On teint un tissu de coton, préalablement blanchi, avec 10% de Rouge au soufre n° 10 (pourcentage exprimé par rapport au poids de la fibre).A cotton fabric, previously bleached, is dyed with 10% sulfur red No. 10 (percentage expressed relative to the weight of the fiber).

On adopte les proportions suivantes pour le bain de teinture:

  • 10% de colorant
  • 10% de sulfure de sodium
  • 10% de chlorure de sodium.
On adopte un rapport de bain de 1 à 10 entre le poids de la fibre et le volume du bain de teinture. On réalise la teinture pendant 1 heure à la température de 95 °C.
Figure imgb0001
 The following proportions are adopted for the dye bath:
  • 10% dye
  • 10% sodium sulfide
  • 10% sodium chloride.
A bath ratio of 1 to 10 is adopted between the weight of the fiber and the volume of the dye bath. Dyeing is carried out for 1 hour at a temperature of 95 ° C.
Figure imgb0001

Pour tous ces bains, on adopte les conditions suivantes:

  • - Température 50 °C
  • - Rapport de bain 1 à 20 (rapport entre le poids de la fibre et le volume du bain).
For all these baths, the following conditions are adopted:
  • - Temperature 50 ° C
  • - Bath ratio 1 to 20 (ratio between the weight of the fiber and the volume of the bath).

On observe une vitesse d'oxydation insuffisante avec les bains A, B et C, l'oxydation totale du coloris n'est, par exemple, pas réalisée après 30 secondes de traitement.An insufficient oxidation rate is observed with baths A, B and C, the total oxidation of the color is, for example, not carried out after 30 seconds of treatment.

Comparativement, l'oxydation réalisée en D est nettement plus rapide; on observe, en effet, dans ce cas, une oxydation totale après 10 secondes de traitement; on constate également que le coloris n'a subi aucune modification de tonalité.Comparatively, the oxidation carried out in D is much faster; indeed, in this case, total oxidation is observed after 10 seconds of treatment; we also note that the color has not undergone any change in tone.

Exemple 2Example 2

On reprend les conditions précédentes. On réalise l'oxydation sur trois parties séparées des fi-bres teintes et rincées, en utilisant respectivement les bains suivants:

Figure imgb0002
We take the previous conditions. Oxidation is carried out on three separate portions of the f i-dyed fibers and rinsed, using the following baths respectively:
Figure imgb0002

Après traitement, l'oxydation réalisée avec les bains A et B est nettement insuffisante. Comparativement, l'oxydation réalisée en C est nettement plus rapide. On constate, cependant, dans ce dernier cas, que le coloris subit un bleuissement important et n'est plus conforme aux spécifications du colorant considéré. On remarque que dans cet exemple il n'y a pas de vanadate dans la composition du bain.After treatment, the oxidation carried out with baths A and B is clearly insufficient. Comparatively, the oxidation carried out in C is much faster. It is noted, however, in the latter case, that the color undergoes significant bluing and no longer complies with the specifications of the dye considered. Note that in this example there is no vanadate in the composition of the bath.

Exemple 3Example 3

On réalise une teinture sur Jigger avec 10% de colorant.We make a dye on Jigger with 10% dye.

Après teinture, on réalise l'oxydation en opérant dans les conditions comparatives suivantes:

  • A. Rinçage par Jigger à l'aide de deux passages dans de l'eau froide.
  • B. Oxydation sur Jigger avec:
    Figure imgb0003
After dyeing, the oxidation is carried out by operating under the following comparative conditions:
  • A. Rinse with Jigger using two passes in cold water.
  • B. Oxidation on Jigger with:
    Figure imgb0003

On réalise deux passages à la température de 50 °C. On observe ur e oxydation rapide et totale de l'ensemble de la matière teinte.Two passages are made at a temperature of 50 ° C. Ur rapid and total oxidation of all of the dyed material is observed.

C. On adopte les mêmes conditions mais réalise l'oxydation avec un bain dépourvu de peroxyde d'hydrogène et contenant:

Figure imgb0004
C. The same conditions are adopted but the oxidation is carried out with a bath devoid of hydrogen peroxide and containing:
Figure imgb0004

On observe, dans ce cas, une oxydation très nettement incomplète de la matière teinte quel que soit le nombre de passages effectués dans le bain oxydant.In this case, very clearly incomplete oxidation of the dyed material is observed regardless of the number of passages made in the oxidizing bath.

Les exemples qui précèdent montrent l'efficacité de l'action combinée du peroxyde d'hydrogène, d'un sel métallique et d'un vanadate alcalin, présents simultanément dans le bain d'oxydation.The foregoing examples show the effectiveness of the combined action of hydrogen peroxide, a metal salt and an alkaline vanadate, present simultaneously in the oxidation bath.

Claims (8)

1. Process for oxidizing the dye of a fabric or fiber dyed with a sulfur dye or a vat dye by means of a hydrogen peroxide solution in presence of a vanadate salt, at a pH comprised between 3 and 6 and at a temperature comprised between 20 and 95 °C, the amounts of hydrogen peroxide and of vanadate salt being comprised, respectively, between 0.1 and 30 g and between 0.05 and 0.5 g per liter of bath, characterized in that the oxidation is carried out in the simultaneous presence of a metal salt selected among copper iron, nickel, cobalt and manganese salts, the amount of said salt being comprised between 0.01 and 1 g per liter of oxidizing bath.
2. Process according to claim 1, characterized in that said metal salt is a copper salt.
3. Process according to claim 1 or 2, characterized in that the vanadate is chosen from the family comprising the alkali metal vanadates and ammonium vanadate.
4. Process according to claim 1, characterized in that the amount of metal salt is between 0.05 and 0.1 g/I.
5. Process according to claim 1, characterized in that the amounts of vanadate are between 0.1 and 0.2 g/I.
6. Process according to claim 1, characterized in that the amount of hydrogen peroxide is between 1 and 5 g/I.
7. Process according to claim 1, characterized in that the oxidation is carried out at a temperature between 40 an 60 °C.
8. Process according to any of claims 1 to 7, characterized in that the dye is Sulfur Red No. 10 (color Index N° 53 228).
EP19850402090 1984-10-31 1985-10-30 Process for the oxidation of sulphur dyestuffs Expired EP0181257B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8416681 1984-10-31
FR8416681A FR2572416B1 (en) 1984-10-31 1984-10-31 IMPROVEMENT IN THE SULFUR DYE OXIDATION PROCESS

Publications (2)

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EP0181257A1 EP0181257A1 (en) 1986-05-14
EP0181257B1 true EP0181257B1 (en) 1988-09-14

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EP19850402090 Expired EP0181257B1 (en) 1984-10-31 1985-10-30 Process for the oxidation of sulphur dyestuffs

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EP (1) EP0181257B1 (en)
JP (1) JPS61502065A (en)
DE (1) DE3564972D1 (en)
FR (1) FR2572416B1 (en)
WO (1) WO1986002676A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03134344A (en) * 1989-10-18 1991-06-07 Mitsubishi Heavy Ind Ltd Gear

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE291426C (en) *
FR1421707A (en) * 1963-12-19 1965-12-17 Du Pont Oxidation of sulfur dyes
US4036586A (en) * 1975-10-16 1977-07-19 E. I. Du Pont De Nemours And Company Process for oxidizing sulfur dyes
DE2914260A1 (en) * 1979-04-09 1980-10-23 Cassella Ag Textile dyeing and printing comprising dye re-oxidn. - in aq. bath contg. soluble vanadate, tungstate or molybdate accelerator and peroxide
US4310332A (en) * 1980-02-07 1982-01-12 Interox Chemicals Limited Oxidation of sulfur dyes

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FR2572416A1 (en) 1986-05-02
WO1986002676A1 (en) 1986-05-09
DE3564972D1 (en) 1988-10-20
EP0181257A1 (en) 1986-05-14
JPS6356354B2 (en) 1988-11-08
FR2572416B1 (en) 1987-09-04
JPS61502065A (en) 1986-09-18

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